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Sample records for monodentate azide anions

  1. Ultrasonically-enhanced preparation, characterization of CaFe-layered double hydroxides with various interlayer halide, azide and oxo anions (CO32-, NO3-, ClO4-).

    Science.gov (United States)

    Szabados, Márton; Varga, Gábor; Kónya, Zoltán; Kukovecz, Ákos; Carlson, Stefan; Sipos, Pál; Pálinkó, István

    2018-01-01

    An ultrasonically-enhanced mechanochemical method was developed to synthesize CaFe-layered double hydroxides (LDHs) with various interlayer anions (CO 3 2- , NO 3 - , ClO 4 - , N 3 - , F - , Cl - , Br - and I - ). The duration of pre-milling and ultrasonic irradiation and the variation of synthesis temperature in the wet chemical step were investigated to obtain the optimal parameters of preparation. The main method to characterize the products was X-ray diffractometry, but infrared and synchrotron-based X-ray absorption spectroscopies as well as thermogravimetric measurements were also used to learn about fine structural details. The synthesis method afforded successful intercalation of the anions, among others the azide anion, a rarely used counter ion providing a system, which enables safe handling the otherwise highly reactive anion. The X-ray absorption spectroscopic measurements revealed that the quality of the interlayered anions could modulate the spatial arrangement of the calcium ions around the iron(III) ions, but only in the second coordination sphere. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Magnetic resonance studies on the copper site of dopamine β-monooxygenase in the presence of cyanide and azide anions

    International Nuclear Information System (INIS)

    Obata, A.; Tanaka, H.; Kawazura, H.

    1987-01-01

    In order to elucidate the coordination state of water molecules in the Cu(II) site of dopamine [(3,4-dihydroxyphenyl)ethylamine] β-monooxygenase, measurements of the paramagnetic 1 H nuclear magnetic relaxation rate of solvent water in the enzyme solution containing cyanide or azide as an exogenous ligand were carried out to obtain the values of intrinsic paramagnetic relaxation rate decrements R/sub p/ 1 and R/sub p/ 2 for the ligand-enzyme 1:1 and 2:1 complexes, respectively. R/sub p/ 1 (percent) values were 53 (pH 5.5) and 52 (pH 7.0) for cyanide and 38 (pH 5.5) and 32 (pH 7.0) for azide, while R/sub p/ 2 (percent) values were 98 (pH 5.5) and 96 (pH 7.0) for azide. Although no R/sub p/ 2 values for cyanide were obtained because of its reducing power at the Cu(II) site, the R/sub p/ 1 and R/sub p/ 2 values obtained above prove that the Cu(II) center has two coordinated water molecules that are exchangeable for exogenous ligands at either pH. Supporting evidence was provided by electron paramagnetic resonance (EPR) titration, in which the enzyme solution containing cyanide-enzyme (1:1) complex in an equal proportion to uncomplexed enzyme gave an observed paramagnetic relaxation rate decrement, R/sub p/, of 23%. Another characteristic of the R/sub p/ 1 and R/sub p/ 2 values was their invariability with respect to pH, indicating that the three-dimensional structure of the Cu(II) site is pH-invariant within the range examined. Binding constants of ligand to enzyme K/sub b/ 1 and K/sub b/ 2 for 1:1 and 2:1 complex formation, respectively, were also determined through an analysis of the R/sub p/ values; it was found that K/sub b/ 1 was larger than K/sub b/ 2 irrespective of pH. On the basis of these results, together with the axial-symmetric EPR parameters of the 1:1 complexes, a possible coordination geometry of the two water molecules in the Cu(II) site of the enzyme is suggested

  3. Sodium Azide

    Science.gov (United States)

    ... Exposure to a large amount of sodium azide by any route may cause these other health effects as well: Convulsions Low blood pressure Loss of consciousness Lung injury Respiratory failure leading to death Slow heart rate ...

  4. PH dependence of the spectral and anion binding properties of iron containing superoxide dismutase from E. coli B. An explanation for the azide inhibition of dismutase activity

    Energy Technology Data Exchange (ETDEWEB)

    Fee, J A; McClune, G J; Lees, A C [Michigan Univ., Ann Arbor (USA). Dept. of Biological Chemistry; Zidovetzki, R; Pecht, I [Weizmann Inst. of Science, Rehovoth (Israel). Dept. of Chemical Immunology

    1981-01-01

    Examination of the optical and EPR properties of the ferric form of the iron containing superoxide dismutase from E.coli B, at pH values ranging from 4.5 to 10.9, has revealed two reversible structural transitions affecting the Fe/sup 3 +/ ion. The apparent pKsub(a) values of these transitions are 5.1+-0.3 and 9.O+-0.3. The binding of azide has been studied over the pH range 4.5 to 10.7; the affinity of the Fe/sup 3 +/ for N/sub 3//sup -/ is independent of pH from 4.5 to approximately 7.5, after which the dissociation constant decreased by a factor of 10 per unit increase in pH. The apparent pKsub(a) which affects N/sub 3//sup -/ binding to the iron is 8.6+-0.2. The association of N/sub 3//sup -/ with the iron has been examined using the temperature-jump method at pH 7.4 and 9.3. The kinetics of ligand association were shown to conform to the minimal mechanism: P-Fe/sup 3 +/ + N/sub 3//sup -/reversible K/sub 1/N/sub 3//sup -/ - P-Fe/sup 3 +/reversible K/sub 2/P-Fe/sup 3 +/ - N/sub 3//sup -/. K/sub 1/ was found to be essentially unaffected by pH whereas K/sub 2/ was much lower at pH 9.3 than at 7.4. The value of K/sub 1/ at pH 7.4 (100 M/sup -1/) corresponds very closely to that obtained for the inhibition constant of azide, 10mM. A scheme is presented in which N/sub 3//sup -/ inhibits the iron containing dismutase by competing with O/sub 2//sup -/ for an anion binding site near, but not on the Fe/sup 3 +/.

  5. Determination of insoluble azides by thermometric titrimetry.

    Science.gov (United States)

    Chagas, A P; Godinho, O E; Costa, J L

    1977-09-01

    A method for determination of azide, based on the thermometric titration of this anion with hydrochloric acid, is described. Although this reaction has a large enthalpy change (DeltaH = -3.6 kcal/ mole), sulphate is added as an endothermic thermometric indicator to improve the end-point. The application of the method to the analysis of insoluble azides has been studied.

  6. Phosphoramidite accelerated copper(I)-catalyzed [3+2] cycloadditions of azides and alkynes

    NARCIS (Netherlands)

    Campbell-Verduyn, Lachlan S.; Mirfeizi, Leila; Dierckx, Rudi A.; Elsinga, Philip H.; Feringa, Ben L.

    2009-01-01

    Monodentate phosphoramidite ligands are used to accelerate the copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and alkynes (CuAAC) rapidly yielding a wide variety of functionalized 1,4-disubstituted-1,2,3-triazoles; Cu(I) and Cu(II) salts both function as the copper source in aqueous

  7. Thermochemistry of organic azides revisited

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Algarra, Manuel; Esteves da Silva, Joaquim C.G.; Hierrezuelo, Jesús; López-Romero, Juan M.; Verevkin, Sergey P.

    2014-01-01

    Highlights: • Pure samples of 4-nitro-phenyl azide, 1-octyl- and 1-decyl-azides were prepared. • Vapour pressures, sublimation and vaporization enthalpies measured by transpiration. • Enthalpy of formation of 1-alkyl azides measured by combustion calorimetry. • Enthalpy of fusion of 4-nitro-phenyl azide measured by DSC. • Experimental gas enthalpies of formation were in agreement with calculated by G4. - Abstract: Highly pure samples of 4-nitro-phenyl azide, 1-octyl azide and 1 decyl-azide were prepared for thermochemical studies. Vapour pressures over the solid and the liquid sample of 4-nitro-phenyl azide have been determined by the transpiration method. The molar enthalpies of vaporization/sublimation for this compound were derived from the temperature dependencies of vapour pressures. The molar enthalpy of fusion of 4-nitro-phenyl azide was measured by DSC. The measured data set for 4-nitro-phenyl azide was successfully checked for internal consistency. Molar enthalpies of vaporization of 1-octyl azide and 1 decyl-azide were measured by transpiration. The molar enthalpies of formation of the liquid 1-octyl azide and 1 decyl-azides were derived from the combustion calorimetry. New experimental results for these organic azides have been used to derive their molar enthalpies of formation in the gas state and for comparison with results from quantum-chemical method G4

  8. Versatile lanthanide-azide complexes with azide/carboxylate/hydroxy mixed bridged chain exhibiting magnetic and luminescent properties

    International Nuclear Information System (INIS)

    Wang Haichao; Xue Min; Guo Qian; Zhao Jiongpeng; Liu Fuchen; Ribas, Joan

    2012-01-01

    Two new lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb for 1 and Tb for 2, isonic=isonicotinate), were obtained in hydrothermal condition. X-ray diffraction analysis indicated the two complexes are isomorphic chain structure in which the Ln III ions are mixed bridged by the azide anions, hydroxyl anions and carboxylate groups of the isonicotinate ligands. Further studies indicated weak antiferromagnetic interactions between the Ln III ions in 1 and 2, and complex 2 exhibit green sensitized Luminescent character of Tb III ion. - Graphical abstract: Two new 1D lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb III for 1 and Tb III for 2, isonic=isonicotinate), were synthesized by hydrothermal reaction and exhibit interesting magnetism and fluorescence properties. Highlights: ► The research provided a new method for synthesizing lanthanide-azide complexes. ► The complexes have an interesting azide/hydroxyl/carboxylate mixed bridged1D chain structure. ► The antiferromagnetic coupling between the complexes and 2 displays green luminescence.

  9. Mutagenic azide metabolite is azidoalanine

    International Nuclear Information System (INIS)

    Owais, W.M.; Rosichan, J.L.; Ronald, R.C.; Kleinhofs, A.; Nilan, R.A.

    1981-01-01

    Sodium axide produces high mutation rates in a number of species. Azide mutagenicity is mediated through a metabolite in barley and bacteria. Many studies showed that azide affects the L-cysteine biosynthesis pathway. Cell-free extracts of Salmonella typhimurium convert azide and O-acetylserine to the mutagenic metabolite. O-acetylserine sulfhydrylase was identified as the enzyme responsible for the metabolite biosynthesis. To confirm the conclusion that the azide metabolite is formed through the β-substitution pathway of L-cysteine, we radioactively labeled the azide metabolite using 14 C-labeled precursors. Moreover, the mutagenic azide metabolite was purified and identified as azidoalanine based on mass spectroscopy and elemental analysis. 26 refs., 3 figs., 1 tab

  10. Thiophene-2-carbonyl azide

    Directory of Open Access Journals (Sweden)

    Michael Findlater

    2013-08-01

    Full Text Available The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å and forms an extended layer structure in the (100 plane, held together via hydrogen-bonding interactions between adjacent molecules. Of particular note is the occurrence of RC—H...N−=N+=NR interactions between an aromatic C—H group and an azide moiety which, in conjunction with a complementary C—H...O=C interaction, forms a nine-membered ring.

  11. Alkaline azide mutagenicity in cowpea

    Energy Technology Data Exchange (ETDEWEB)

    Mahna, S K; Bhargava, Anubha; Mohan, Lalit [Cytogenetics and Mycology Laboratory, Department of Botany, Government College, Ajmer (India)

    1990-07-01

    Sodium azide is known as a potent mutagen in cereals and legumes. It is very effective in acidic medium in barley. Here an attempt is made to measure the effectiveness of sodium azide in alkaline medium (pH 7.4) on cowpea (Vigna unguiculata (L.) Walp., variety FS-68). Seeds pre-soaked in distilled water for 5 hours were treated with different concentrations (10{sup -6}, 10{sup -5}, 10{sup -4} and 10{sup -3}M) of sodium azide (NaN{sub 3}) for 4 hours at 28{+-} 2 deg. C. Bottles were intermittently shaken, then the seeds were thoroughly washed in running tap water and subsequently planted in pots. The treatment caused significant biological damage such as reduction in seed germination, length of root and shoot, number of nodules and pods per plant and morphological leaf variations. Morphological, as well as chlorophyll mutants, were detected in M{sub 2}.

  12. Alkaline azide mutagenicity in cowpea

    International Nuclear Information System (INIS)

    Mahna, S.K.; Bhargava, Anubha; Mohan, Lalit

    1990-01-01

    Sodium azide is known as a potent mutagen in cereals and legumes. It is very effective in acidic medium in barley. Here an attempt is made to measure the effectiveness of sodium azide in alkaline medium (pH 7.4) on cowpea (Vigna unguiculata (L.) Walp., variety FS-68). Seeds pre-soaked in distilled water for 5 hours were treated with different concentrations (10 -6 , 10 -5 , 10 -4 and 10 -3 M) of sodium azide (NaN 3 ) for 4 hours at 28± 2 deg. C. Bottles were intermittently shaken, then the seeds were thoroughly washed in running tap water and subsequently planted in pots. The treatment caused significant biological damage such as reduction in seed germination, length of root and shoot, number of nodules and pods per plant and morphological leaf variations. Morphological, as well as chlorophyll mutants, were detected in M 2

  13. Design, Testing and Kinetic Analysis of Bulky Monodentate Phosphorus Ligands in the Mizoroki-Heck Reaction

    NARCIS (Netherlands)

    Dodds, Deborah L.; Boele, Maarten D. K.; van Strijdonck, Gino P. F.; de Vries, Johannes G.; van Leeuwen, Piet W. N. M.; Kamer, Paul C. J.

    A series of new monodentate phosphane ligands 2 have been evaluated in the MizorokiHeck arylation reaction of iodobenzene and styrene and compared with our previously reported ligands, 1, 3 and 4. The concept of rational ligand design is discussed, and we describe how the performance of this new

  14. Asymmetric hydrogenation of quinolines catalyzed by iridium complexes of monodentate BINOL-derived phosphoramidites

    NARCIS (Netherlands)

    Mrsic, Natasa; Lefort, Laurent; Boogers, Jeroen A. F.; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.; Mršić, Nataša

    The monodentate BINOL-derived phosphoramidite PipPhos is used as ligand for the iridium-catalyzed asymmetric hydrogenation of 2- and 2,6-substituted quinolines. If tri-ortho-tolylphosphine and/or chloride salts are used as additives enantioselectivities are strongly enhanced up to 89%. NMR indicates

  15. Thermodynamics of synergistic extraction of hexavalent plutonium with HPMBP and neutral donors: monodentate versus bidentate

    International Nuclear Information System (INIS)

    Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.; Jain, H.C.

    1996-01-01

    Synergistic extraction of hexavalent plutonium was studied from HNO 3 medium (0.05 M) with 1-phnyl, 3-methyl, 4-benzoyl, pyrazolone-5 (HPMBP) and different monodentate neutral donors viz. diphenyl sulphoxide (DPSO), tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) using benzene as a diluent. Thermodynamic parameters (ΔG, ΔH, ΔS) evaluated by performing the experiments at various fixed temperatures (288 K to 318 K) were compared with those reported previously for the bidentate neutral donors (DBDECMP, DHDECMP and CMPO). The net enthalpy changes were negative and comparable. The monodentate neutral donors, however, showed a larger decrease in the entropy values. Further, the negative values of enthalpy and entropy changes indicated that the organic adduct formation is an addition reaction as reported ealier for the bidentate donors. (orig.)

  16. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    International Nuclear Information System (INIS)

    Zheng, Yijun; Cui, Jiaxi; Ikeda, Taichi

    2015-01-01

    Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N 3 -SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N 3 -SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10 −10 mol cm −2 and 4.6 ± 0.3 × 10 −10 mol cm −2 , respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N 3 -SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

  17. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Yijun; Cui, Jiaxi [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Ikeda, Taichi, E-mail: IKEDA.Taichi@nims.go.jp [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 (Japan)

    2015-11-15

    Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N{sub 3}-SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N{sub 3}-SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10{sup −10} mol cm{sup −2} and 4.6 ± 0.3 × 10{sup −10} mol cm{sup −2}, respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N{sub 3}-SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

  18. Controlling hazardous chemicals in microreactors: Synthesis with iodine azide

    Directory of Open Access Journals (Sweden)

    Johan C. Brandt

    2009-06-01

    Full Text Available Aromatic aldehydes have been converted into the corresponding carbamoyl azides using iodine azide. These reactions have been performed safely under continuous flow reaction conditions in microreactors.

  19. AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

    Institute of Scientific and Technical Information of China (English)

    Hong-kun Li; Jing-zhi Sun; An-jun Qin; Ben Zhong Tang

    2012-01-01

    The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field.This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles (PTAs) with linear and hyperbranched structures.The Cu(Ⅰ)-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.

  20. Fourier transform infrared spectroscopy of azide and cyanate ion pairs in AOT reverse micelles

    Science.gov (United States)

    Owrutsky, Jeffrey C.; Pomfret, Michael B.; Barton, David J.; Kidwell, David A.

    2008-07-01

    Evidence for ion pair formation in aqueous bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles (RMs) was obtained from infrared spectra of azide and cyanate with Li+, Na+, K+, and NH4+ counterions. The anions' antisymmetric stretching bands near 2000 cm-1 are shifted to higher frequency (blueshifted) in LiAOT and to a lesser extent in NaAOT, but they are very similar to those in bulk water with K+ and NH4+ as the counterions. The shifts are largest for low values of wo=[water]/[AOT] and approach the bulk value with increasing wo. The blueshifts are attributed to ion pairing between the anions and the counterions. This interpretation is reinforced by the similar trend (Li+>Na+>K+) for producing contact ion pairs with the metal cations in bulk dimethyl sulfoxide (DMSO) solutions. We find no evidence of ion pairs being formed in NH4AOT RMs, whereas ammonium does form ion pairs with azide and cyanate in bulk DMSO. Studies are also reported for the anions in formamide-containing AOT RMs, in which blueshifts and ion pair formation are observed more than in the aqueous RMs. Ion pairs are preferentially formed in confined RM systems, consistent with the well established ideas that RMs exhibit reduced polarity and a disrupted hydrogen bonding network compared to bulk water and that ion-specific effects are involved in mediating the structure of species at interfaces.

  1. PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

    2005-01-01

    A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the

  2. Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3). [applications to spacecraft fuel cells

    Science.gov (United States)

    Sheridan, P. S.

    1980-01-01

    A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

  3. Thio-phene-2-carbonyl azide.

    Science.gov (United States)

    Hsu, Gene C; Singer, Laci M; Cordes, David B; Findlater, Michael

    2013-01-01

    The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å) and forms an extended layer structure in the (100) plane, held together via hydrogen-bonding inter-actions between adjacent mol-ecules. Of particular note is the occurrence of RC-H⋯N(-)=N(+)=NR inter-actions between an aromatic C-H group and an azide moiety which, in conjunction with a complementary C-H⋯O=C inter-action, forms a nine-membered ring.

  4. Sodium Azide Associated Acute Hyperkalemia in a Swine Model of Sodium Azide Toxicity

    Science.gov (United States)

    2017-06-16

    Sodium Azide Toxicity presented at/published to SURF , San Antonio, TX, 16 June 2017 in accordance with MDWI 41-108, has been approved and assigned local...Surgical Center (WHASC) internship and residency programs. 3. Please know that if you are a Graduate Health Sciences Education student and your... waves on electrocardiogram and continued acidosis (lactate mean 6.7 mmo/L). Statistics: Repeated measures ANOVA was used to determine statistically

  5. Vapor pressures and enthalpies of vaporization of azides

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Emel'yanenko, Vladimir N.; Algarra, Manuel; Manuel Lopez-Romero, J.; Aguiar, Fabio; Enrique Rodriguez-Borges, J.; Esteves da Silva, Joaquim C.G.

    2011-01-01

    Highlights: → We prepared and measured vapor pressures and vaporization enthalpies of 7 azides. → We examined consistency of new and available in the literature data. → Data for geminal azides and azido-alkanes selected for thermochemical calculations. - Abstract: Vapor pressures of some azides have been determined by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. The measured data sets were successfully checked for internal consistency by comparison with vaporization enthalpies of similarly structured compounds.

  6. Surviving a massive sodium azide poisoning with toxic cardiomyopathy

    Directory of Open Access Journals (Sweden)

    P. Overtchouk

    2015-01-01

    Full Text Available Sodium azide poisoning is rare (~50 case reports but can be quickly fatal. A systematic review reported the fatal dose in humans to be over 10 mg/kg1. A 69 year-old female was admitted to our hospital for voluntary sodium azide poisoning. She ingested a massive dose of a soup spoon (15 g of pure sodium azide powder with intention to commit suicide without any co-intoxication. Within minutes, she felt nauseous and had several vomiting. She was immediately brought to the hospital.

  7. Effectiveness of sodium azide alone compared to sodium azide in combination with methyl nitrosurea for rice mutagenesis

    Science.gov (United States)

    Rice seeds of the temperate japonica cultivar Kitaake were mutagenized with sodium azide alone and in combination with methyl nitrosourea. Using the reduced representation sequencing method Restriction Enzyme Sequence Comparative Analysis (RESCAN), the mutation densities, types and local sequence co...

  8. Applications of Azide-Based Bioorthogonal Click Chemistry in Glycobiology

    Directory of Open Access Journals (Sweden)

    Xiu Zhang

    2013-06-01

    Full Text Available Click chemistry is a powerful chemical reaction with excellent bioorthogonality features: biocompatible, rapid and highly specific in biological environments. For glycobiology, bioorthogonal click chemistry has created a new method for glycan non-invasive imaging in living systems, selective metabolic engineering, and offered an elite chemical handle for biological manipulation and glycomics studies. Especially the [3 + 2] dipolar cycloadditions of azides with strained alkynes and the Staudinger ligation of azides and triarylphosphines have been widely used among the extant click reactions. This review focuses on the azide-based bioorthogonal click chemistry, describing the characteristics and development of these reactions, introducing some recent applications in glycobiology research, especially in glycan metabolic engineering, including glycan non-invasive imaging, glycomics studies and viral surface manipulation for drug discovery as well as other applications like activity-based protein profiling and carbohydrate microarrays.

  9. Conversion of Azides into Diazo Compounds in Water

    Science.gov (United States)

    Chou, Ho-Hsuan; Raines, Ronald T.

    2013-01-01

    Diazo compounds are in widespread use in synthetic organic chemistry, but have untapped potential in chemical biology. We report on the design and optimization of a phosphinoester that mediates the efficient conversion of azides into diazo compounds in phosphate buffer at neutral pH and room temperature. High yields are maintained in the presence of common nucleophilic or electrophilic functional groups, and reaction progress can be monitored by colorimetry. As azido groups are easy to install and maintain in biopolymers or their ligands, this new mode of azide reactivity could have substantial utility in chemical biology. PMID:24053717

  10. Ultrafast Infrared and UV-vis Studies of the Photochemistry of Methoxycarbonylphenyl Azides in Solution

    OpenAIRE

    Xue, Jiadan; Luk, Hoi Ling; Eswaran, S. V.; Hadad, Christopher M.; Platz, Matthew S.

    2012-01-01

    The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a) and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitre...

  11. Morphogical effects of sodium azide on tomato ( Lycopersicon ...

    African Journals Online (AJOL)

    Dry seeds of tomato (Lycopersicon esculentun Mill), varieties T106, T244 and T420 obtained from the Institute of Agriculture Research, Ahmadu Bello University Zaria, Nigeria were treated with sodium azide at concentrations of 1.0, 2.0 and 4.0 mM aimed at determining the effects of the mutagen on the morphological ...

  12. Cyanogen Azide. Ionization Potentials and Ab Initio SCF MO Calculation

    DEFF Research Database (Denmark)

    Bak, Börge; Jansen, Peter; Stafast, Herbert

    1975-01-01

    The Ne(I) and He(I) photoelectron(PE) spectra of cyanogen azide, NCN3, have been recorded at high resolution. Their interpretation is achieved by comparison with the PE spectrum of HN3 and an ab initio LCGO SCF MO calculation. Deviations from Koopmans' theorem of quite different magnitudes...

  13. Azide- and alkyne-derivatised α-amino acids

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Pedersen, D.S.

    2012-01-01

    With the emergence of the copper-catalysed Huisgen cycloaddition the use of azide- and alkyne-derivatised α-amino acids has found widespread use within most chemistry disciplines. Despite a growing interest in these building blocks researchers are struggling to identify the best way for their syn......With the emergence of the copper-catalysed Huisgen cycloaddition the use of azide- and alkyne-derivatised α-amino acids has found widespread use within most chemistry disciplines. Despite a growing interest in these building blocks researchers are struggling to identify the best way...... for their synthesis. In this review we have compiled available methods for synthesising optically active azide- and alkyne-derivatised α-amino acids that can be prepared from readily available α-amino acids. We highlight a number of commonly overlooked problems associated with existing methods and direct attention...... to unexplored possibilities. Azide- and alkyne-derivatised α-amino acids are finding widespread use within most chemistry disciplines. However, it is far from clear what the best way for the synthesis of these useful building blocks is. Herein we show the available methods for synthesis of optically active...

  14. Thermal Decompositon Studies Of Pre-Irradiated Nickel (II) Azides ...

    African Journals Online (AJOL)

    The effect of pre-irradiation on the thermal decomposition of three samples of nickel (II) azide was studied. It was found that the rates of thermal decomposition of Ni(OH)N3 increased substantially with increase in pre-irradiation dosage. The initial reaction rates change from time-dependant nucleation law for the unirradiated ...

  15. Effects of sodium azide on yield parameters of groundnut (Arachis ...

    African Journals Online (AJOL)

    GREGO

    2007-03-19

    Mar 19, 2007 ... Cowpea and mungbean improvement by mutation induction Mutation Breeding Newsletter, 21: 9. Gregory WC (1955). X-ray breeding of peanuts Arachis hypogaea L.,. Agron. J. 47: 394-399. Kleinhofs W, Sander C (1975). Azide mutagenesis in Barley. Third. Barley Genetics Symp. Garching. Proceedings of ...

  16. Preparation and photoluminescence enhancement in terbium(III ternary complexes with β-diketone and monodentate auxiliary ligands

    Directory of Open Access Journals (Sweden)

    Devender Singh

    2016-12-01

    Full Text Available A series of new solid ternary complexes of terbium(III ion based on β-diketone ligand acetylacetone (acac and monodentate auxiliary ligands (aqua/urea/triphenylphosphineoxide/pyridine-N-oxide had been prepared. The structural characterizations of synthesized ternary compounds were studied by means of elemental analysis, infrared (IR, and proton nuclear magnetic resonance (NMR spectral techniques. The optical characteristics were investigated with absorption as well as photoluminescence spectroscopy. Thermal behavior of compounds was examined by TGA/DTA analysis and all metal complexes were found to have good thermal stability. The luminescence decay time of complexes were also calculated by monitoring at emission wavelength corresponding to 5D4 → 7F5 transition. A comparative inspection of the luminescent behavior of prepared ternary compounds was performed in order to determine the function of auxiliary ligands in the enhancement of luminescence intensity produced by central terbium(III ion. The color coordinates values suggested that compounds showed bright green emission in visible region in electromagnetic spectrum. Complexes producing green light could play a significant role in the fabrication of efficient light conversion molecular devices for display purposes and lightning systems.

  17. A Direct Comparison of Azide and Nitrile Vibrational Probes

    Science.gov (United States)

    Gai, Xin Sonia; Coutifaris, Basil A.; Brewer, Scott H.; Fenlon, Edward E.

    2011-01-01

    The synthesis of 2′-azido-5-cyano-2′-deoxyuridine, N3CNdU (1), from trityl-protected 2′-amino-2′-deoxyuridine was accomplished in four steps with a 12.5% overall yield. The IR absorption positions and profiles of the azide and nitrile group of N3CNdU were investigated in 14 different solvents and water/DMSO solvent mixtures. The azide probe was superior to the nitrile probe in terms of its extinction coefficient, which is 2–4 times larger. However, the nitrile IR absorbance profile is generally less complicated by accidental Fermi resonance. The IR frequencies of both probes undergo a substantial red shift upon going from water to aprotic solvents such as THF or DMSO. DFT calculations supported the hypothesis that the molecular origin of the higher observed frequency in water is primarily due to hydrogen bonds between the probes and water molecules. PMID:21336362

  18. Targeted Diazotransfer Reagents Enable Selective Modification of Proteins with Azides.

    Science.gov (United States)

    Lohse, Jonas; Swier, Lotteke J Y M; Oudshoorn, Ruben C; Médard, Guillaume; Kuster, Bernhard; Slotboom, Dirk-Jan; Witte, Martin D

    2017-04-19

    In chemical biology, azides are used to chemically manipulate target structures in a bioorthogonal manner for a plethora of applications ranging from target identification to the synthesis of homogeneously modified protein conjugates. While a variety of methods have been established to introduce the azido group into recombinant proteins, a method that directly converts specific amino groups in endogenous proteins is lacking. Here, we report the first biotin-tethered diazotransfer reagent DtBio and demonstrate that it selectively modifies the model proteins streptavidin and avidin and the membrane protein BioY on cell surface. The reagent converts amines in the proximity of the binding pocket to azides and leaves the remaining amino groups in streptavidin untouched. Reagents of this novel class will find use in target identification as well as the selective functionalization and bioorthogonal protection of proteins.

  19. INDUCED-GROWTH AND YIE BY SODIUM AZIDE IN TOMATO ...

    African Journals Online (AJOL)

    userpc

    ABSTRACT. The mutagenic effect of various concentra traits of three varieties of tomato was inve quantity of the traits of economic importa. Roma, UC and a Local variety were treated. (0.1mM, 1.0 mM, 2.0 mM and 0.0 mM as con seasons. The results obtained revealed high various concentrations of sodium azide on.

  20. Glycosyl azide-a novel substrate for enzymatic transgycosylations

    Czech Academy of Sciences Publication Activity Database

    Fialová, Pavla; Carmona, A. T.; Robina, I.; Ettrich, R.; Sedmera, Petr; Přikrylová, Věra; Hušáková, Lucie; Křen, Vladimír

    2005-01-01

    Roč. 46, - (2005), s. 8715-8718 ISSN 0040-4039 R&D Projects: GA ČR GA203/05/0172; GA MŠk OC D25.002 Grant - others:GA KONTAKT 1862/04 Institutional research plan: CEZ:AV0Z50200510 Keywords : enzyme catalysis * glycosyl azide * molecular modelling Subject RIV: EE - Microbiology, Virology Impact factor: 2.477, year: 2005

  1. Sodium azide mutagenesis in wheat: Mutants with golden glumes

    International Nuclear Information System (INIS)

    Siddiqui, K.A.; Jafri, K.A.; Arain, M.A.

    1989-01-01

    In bread wheat, Triticum aestivum L. (2n=6x=42, AABBDD), detection of induced mutations is hampered by the presence of duplicate and triplicate genes. Induced changes in spike characteristics are known, but mutants with changed glume colour do not seem to have been reported. Physical mutagens such as gamma rays, thermal neutrons and fast neutrons, and chemical mutagens like EMS, El, dES and NEH have been extensively used for induction of mutations in bread wheat but it seems as if these mutagens did not induce mutants with changed glume colour. We used sodium azide for inducing mutations in the widely adapted cultivar 'Sonalika', which is characterized by brown glume colour. Presoaked seeds were treated with 0.2M sodium azide for 3 hours. Three spikes were harvested from each M 1 plant. M 2 generation was space-planted as spike progeny. We were successful in identifying 3 mutants with golden glumes. The mutants resemble 'Sonalika' in other spike characteristics. The mutants glume colour was confirmed in M 3 . The mutants were also evaluated for agronomically important characteristics. Some characters were significantly different from the parent. Glume colours may be useful as genetic markers since such characters are less influenced by the environment. Our investigation confirms that also agronomically useful genetic variation may be readily induced in bread wheat through sodium azide

  2. Determination of azide in biological fluids by use of electron paramagnetic resonance

    International Nuclear Information System (INIS)

    Minakata, Kayoko; Suzuki, Osamu

    2005-01-01

    A simple and sensitive method has been developed for the determination of azide ion (N 3 - ) in biological fluids and beverages. The procedure was based on the formation of a ternary complex Cu(N 3 ) 2 (4-methylpyridine) x in benzene, followed by its detection by electron paramagnetic resonance. The complex in benzene showed a characteristic four-peak hyperfine structure with a g-value of 2.115 at room temperature. Cu 2+ reacted with N 3 - most strongly among common metals found in biological fluids. Several anions and metal ions in biological fluids did not interfere with the determination of N 3 - in the presence of large amounts of Cu 2+ and oxidants. In the present method, N 3 - at the concentration from 5 μM to 2 mM in 100 μl solution could be determined with the detection limit of 20 ng. The recoveries were more than 95% for N 3 - added to 100 μl of blood, urine, milk and beverages at 200 μM. Our method is recommendable because it takes less than 10 min to determine N 3 - and the produced complex is quite stable

  3. An enzymatic method for determination of azide and cyanide in aqueous phase.

    Science.gov (United States)

    Wan, Nan-Wei; Liu, Zhi-Qiang; Xue, Feng; Zheng, Yu-Guo

    2015-11-20

    A halohydrin dehalogenase (HHDH-PL) from Parvibaculum lavamentivorans DS-1 was characterized and applied to determine azide and cyanide in the water. In this methodology, HHDH-PL catalysed azide and cyanide to react with butylene oxide and form corresponding β-substituted alcohols 1-azidobutan-2-ol (ABO) and 3-hydroxypentanenitrile (HPN) that could be quantitatively detected by gas chromatograph. The detection calibration curves for azide (R(2)=0.997) and cyanide (R(2)=0.995) were linear and the lower limits of detection for azide and cyanide were 0.1 and 0.3mM, respectively. Several other nucleophiles were identified having no effect on the analysis of azide and cyanide, excepting nitrite which influenced the detection of cyanide. This was the first report of a biological method to determine the inorganic azide and cyanide by converting them to the measurable organics. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. 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.

  5. 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.

  6. Anion-Dependent Exocyclic Mercury(II) Coordination Polymers of Bis-dithiamacrocycle

    Energy Technology Data Exchange (ETDEWEB)

    Siewe, Arlette Deukam; Kim, Seul Gi; Choi, Kyu Seong [Kyungnam University, Changwon (Korea, Republic of); Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of)

    2014-09-15

    Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}-Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}- macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer [Hg{sub 2}(L)I{sub 4}]·CHCl{sub 3}n in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer ([Hg{sub 2}(L)(DMF){sub 6}](ClO{sub 4}){sub 4}·2DMF)n instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure.. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies

  7. Radiation-chemical decomposition of heavy metal azides - II. Silver azide radiolysis scheme

    International Nuclear Information System (INIS)

    Ryabykh, S.M.

    1987-01-01

    As a result of complex studies on the nature and properties of final products and intermediate particles using a wide number of experimental topography and radiolysis kinetics methods, we offer the AgN 3 radiolysis scheme including the following stages: homogeneous excitation of electron subsystem with 'hot' electrons and holes formed; 'hot' electron and hole thermalization with possible formation of N 4 - radical in volume on the point defects; electron localization on the immobile structural defects whose neighbourhood is rich in the mobile positively charged point defects; metal particle formation due to electrostatic attraction of the nearby mobile defect to the localized electron, with no thermal excitation; metal particle growth, according to both the diffusional mechanism of delivering the volume of corresponding positively charged point defect with consequent electron capture, and by decomposing anions on the interphase with the consequent border layer cation addition to the growing metal particle, interior space formation in the volume by disintegrating 'hot' excitons into ion defect pairs; nitrogen formation on the exterior and interior surfaces, as well as those formed by radiation, either by trapping the hole by surface cation vacancy or by removing the surface cation of the hole with the consequent addition of the second hole to the Vsub(F)-center, and by disintegrating the activated complex into three nitrogen molecules. For the above stages the characteristic parameters are determined by means of direct measurement and calculation. The kinetics and energy conditions of the process are also found. (author)

  8. The intriguing enhancement of chloroperoxidase mediated one-electron oxidations by azide, a known active-site ligand

    International Nuclear Information System (INIS)

    Andrew, Daniel; Hager, Lowell; Manoj, Kelath Murali

    2011-01-01

    Highlights: ► Azide is a well known heme–enzyme active site ligand and inhibitor. ► Herein, azide is reported to enhance a set of heme–enzyme mediated reactions. ► This effect is disconnected from native enzyme–azide binding. ► Azide could enhance heme–enzyme reactions via a newly proposed mechanism. ► Azide contained in reagents could impact reaction outcomes in redox biochemistry. -- Abstract: Azide is a well-known inhibitor of heme–enzymes. Herein, we report the counter-intuitive observation that at some concentration regimes, incorporation of azide in the reaction medium enhances chloroperoxidase (CPO, a heme–enzyme) mediated one-electron abstractions from several substrates. A diffusible azidyl radical based mechanism is proposed for explaining the phenomenon. Further, it is projected that the finding could have significant impact on routine in situ or in vitro biochemistry studies involving heme–enzyme systems and azide.

  9. Single-step azide introduction in proteins via an aqueous diazo transfer

    NARCIS (Netherlands)

    van Dongen, S.F.M.; Teeuwen, R.L.M.; Nallani, M.; van Berkel, S.S.; Cornelissen, J.J.L.M.; Nolte, R.J.M.; van Hest, J.C.M.

    The controlled introduction of azides in proteins provides targetable handles for selective protein manipulation. We present here an efficient diazo transfer protocol that can be applied in an aqueous solution, leading to the facile introduction of azides in the side chains of lysine residues and at

  10. Single-Step Azide Introduction in Proteins via an Aqueous Diazo Transfer

    NARCIS (Netherlands)

    van Dongen, Stijn; Teeuwen, R.L.M.; Nallani, Madhavan; van Berkel, S.S; Cornelissen, Jeroen Johannes Lambertus Maria; Nolte, Roeland; van Hest, Jan

    2009-01-01

    The controlled introduction of azides in proteins provides targetable handles for selective protein manipulation. We present here an efficient diazo transfer protocol that can be applied in an aqueous solution, leading to the facile introduction of azides in the side chains of lysine residues and at

  11. Polarographic studies about indium (III) behaviour in aqueous media of sodium azide

    International Nuclear Information System (INIS)

    Tokoro, R.

    1988-01-01

    The present study shows some polarographic behavior of indium (III) in azide media that is close those observed in a thiocyanate solution. The presence of azide ligand decreases the overpotential in the discharge of indium whose catalytic character can be explained by formation of an azide bridge between electrode and indium (III) increasing the speed of electron transfer. The discharge of indium in azide media is diffusion controlled. As the azide concentration is increased the half wave potential displaces in the cathodic direction. This displacement is due to complex formation. The number of electrons, n, involved in the total process was estimates by the reversible polarographic equation to be 2,7. The potentiostatic coulometry of indium in azide/hydrazoic acid buffer showed a catalytic process where the chemistry regeneration was performed by reaction of hydrazoic acid and indium amalgam. The electrochemistry evidence was the constancy of current as the electrolysis proceeded. The chemistry aspect was the presence of ammonium cation in electrolysed solution. The catalytic process with chemistry regeneration and the formation of a bridge by azide could explain the higher value of current in azide media compared to perchlorate solution. (author) [pt

  12. Polymerization of nitrogen in cesium azide under modest pressure

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoli, E-mail: use126126@126.com, E-mail: lijianfu@lyu.edu.cn [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Beijing Computational Science Research Center, Beijing 100084 (China); State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012 (China); Li, Jianfu, E-mail: use126126@126.com, E-mail: lijianfu@lyu.edu.cn [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Department of Physics and Materials Science, City University of Hong Kong (Hong Kong); Zhu, Hongyang [State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012 (China); Chen, Li [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Lin, Haiqing [Beijing Computational Science Research Center, Beijing 100084 (China)

    2014-07-28

    Alkali metal azides can be used as starting materials in the synthesis of polymeric nitrogen, a potential high-energy-density material. The structural evolutionary behaviors of nitrogen in CsN{sub 3} have been studied up to 200 GPa using particle swarm optimization structure search combining with density functional theory. Three stable new phases with C2/m, P2{sub 1}/m, and P-1 structure at pressure of 6, 13, and 51 GPa are identified for the first time. The phase transition to chain like structure (P-1 phase) occurs at a modest pressure 51 GPa, the azide ions N{sub 3}{sup −} (linear chains of three N atoms with covalent bonds and interact weakly with each other) begin to show remarkable polymeric N properties in the CsN{sub 3} system. Throughout the stable pressure range, the structure is metallic and consists of N atoms in sp{sup 2} hybridizations. Our study completes the structural evolution of CsN{sub 3} under pressure and reveals that the introduced Cs atoms are responsible for the decreased synthesis pressure comparing to pure molecular nitrogen under compression.

  13. Evolving Structural Diversity and Metallicity in Compressed Lithium Azide

    KAUST Repository

    Prasad, Dasari L. V. K.

    2013-10-10

    In pursuit of new stable nitrogen-rich phases and of a possible insulator-metal transition, the ground-state electronic structure of lithium azide, LiN3, is investigated from 1 atm to 300 GPa (∼2-fold compression) using evolutionary crystal structure exploration methods coupled with density functional theoretical calculations. Two new LiN3 phases, containing slightly reduced and well-separated N2 units, are found to be enthalpically competitive with the known lithium azide crystal structure at 1 atm. At pressures above 36 GPa nitrogen-rich assemblies begin to evolve. These incorporate NN bond formation beyond that in N2 or N3 -. N6 rings and infinite one-dimensional linear nitrogen chains (structural analogues to polyacetylene) appear. Above 200 GPa quasi-one- and two-dimensional extended puckered hexagonal and decagonal nitrogen layers emerge. The high-pressure phase featuring linear chains may be quenchable to P = 1 atm. With increasing pressure the progression in electrical conductivity is from insulator to metal. © 2013 American Chemical Society.

  14. Taming tosyl azide: the development of a scalable continuous diazo transfer process.

    Science.gov (United States)

    Deadman, Benjamin J; O'Mahony, Rosella M; Lynch, Denis; Crowley, Daniel C; Collins, Stuart G; Maguire, Anita R

    2016-04-07

    Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diazo transfer reactions tosyl azide was generated and used in a telescoped flow process, to mitigate the risks associated with handling potentially explosive reagents on scale. The in situ formed tosyl azide was used to rapidly perform diazo transfer to a range of acceptors, including β-ketoesters, β-ketoamides, malonate esters and β-ketosulfones. An effective in-line quench of sulfonyl azides was also developed, whereby a sacrificial acceptor molecule ensured complete consumption of any residual hazardous diazo transfer reagent. The telescoped diazo transfer process with in-line quenching was used to safely prepare over 21 g of an α-diazocarbonyl in >98% purity without any column chromatography.

  15. Effect of sodium azide addition and aging storage on casein micelle size

    Science.gov (United States)

    Sinaga, H.; Deeth, H.; Bhandari, B.

    2018-02-01

    Casein micelles affected most of milk properties, therefore the use sodium azide as milk preservation is not expected to alter milk properties during storage, including the casein micelle size. The aim of this study was to analyse casein micelle size after the addition of sodium azide during storage. The experiment was performed as a complete block randomised design with three replications. The addition of 0.02-0.10% Na-azide do not lead to any noticeable differences in average casein size at the same day and show similar trend after 14 day-storage. At concentration of 0.02% sodium azide (Na-azide), the size of pasteurised milk did not change up to 12 days, while the size of raw skim milk slightly increased by ageing time at day 5. The treated concentration did not affect the size distribution, except for milk with 0.02% Na-azide which had narrower distribution compared to other treated and control milk. The finding from this study suggests that the role of Na-azide in this experiments during storage at 4°C is only for preventing the microbial growth.

  16. Polarografic study about the complex formation between indium (III) and sodium azide, in aqueous media

    International Nuclear Information System (INIS)

    Tokoro, R.; Bertotti, M.

    1988-01-01

    The present work is a branch of the main work concerned with the complex formation between several metal cations and azide ligand in aqueous media. The polarographic behavior of indium in azide system showed the tendency of complexation. Using polarographic method to determine the half potential of indium at each analytical concentration afforded experimental data to evaluate the constants. The azide concentrations was modified from 1 m to 100 m , the ionic strength held at 2,0 M with sodium perchlorate, indium concentration 7.892 x 10 -4 M, and temperature kept constant at 25,0 0 C. (author) [pt

  17. Effects of sodium azide on the abundance of prokaryotes and viruses in marine samples.

    Directory of Open Access Journals (Sweden)

    Christian Winter

    Full Text Available Flow cytometry is set to become the standard method for enumerating prokaryotes and viruses in marine samples. However, the samples need to be flash-frozen in liquid nitrogen directly after aldehyde fixation. Because liquid nitrogen may not always be available, we tested the potential of sodium azide as a preservative for prokaryotes and viruses in marine samples as a possible alternative. For that we conducted incubation experiments with untreated and sodium azide treated marine water samples at 4°C and room temperature. The data indicate that sodium azide cannot be used to maintain marine samples used for the enumeration of prokaryotes and viruses.

  18. Some organodioxygen complexes of molybdenum(VI), tungsten(VI), zinc(II) and cadmium(II) containing some monodentate and multidentate ligands

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Leo Man Lin; Grouse, Karen A.; Mariotto, Gino

    2003-08-01

    Several novel organodioxygen complexes of the type [M(O)(O 2 ) 2 L](MMo(VI), W(VI)) and [M'(O 2 )L](M'= Cd(II) and Zn(II)) have been synthesized using monodentate, bidentate and tridentate ligands, L pyridine, picolinic acid, diethylenetriamine, 1,2-phenylenediamine, triphenylphosphine oxide. These complexes were characterized by elemental analyses, conductivity measurements, infrared, Raman spectral studies. For dioxygen complexes, the v(O=O) stretches of the superoxo moities were only Raman active, because of apparent linearity of the M-O 2 moieties, giving peaks at 1020-1030 cm -1 . The complexes were all thermodynamically stable. The dioxygen complexes containing bidentate co-ligands were found to show oxygen transfer reactions to various organic and inorganic substrates. Mechanisms have been postulated. (author)

  19. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Czech Academy of Sciences Publication Activity Database

    Hemming, K.; Chambers, Christopher S.; Jamshaid, F.; O´Gorman, Paul A.

    2014-01-01

    Roč. 19, č. 10 (2014), s. 16737-16756 ISSN 1420-3049 Institutional support: RVO:61388971 Keywords : azide * cycloadditions * benzodiazepines Subject RIV: CC - Organic Chemistry Impact factor: 2.416, year: 2014

  20. Mutagenic effects of sodium azide and γ-irradiation in Pisum

    International Nuclear Information System (INIS)

    Sander, C.; Muehlbauer, F.J.

    1977-01-01

    Sodium azide was an effective mutagen in Pisum when used at a concentration of 10 -3 M and at pH 3. Effects on dry, sound seeds of 'Juneau' so treated for 3 or 4 hr and for 3 hr in the presence of oxygen were compared with responses to 5, 10 and 20 kR of γ-rays for evaluating relative effectiveness in producing mutants. Leaf aberrations were observed on γ-irradiated plants but not on azide-treated plants, an indication that azide did not cause chromosome damage. At the treatment levels used, sodium azide was as effective in total yield of mutants but produced fewer stunted and variously deformed plants than γ-rays. (author)

  1. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun; Ajitha, Manjaly John; Lang, Ming; Huang, Kuo-Wei; Wang, Jian

    2017-01-01

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha

  2. Crystal structures and DFT calculations of mixed chloride-azide zinc(II) and chloride-isocyanate cadmium(II) complexes with the condensation product of 2-quinolinecarboxaldehyde and Girard's T reagent

    Science.gov (United States)

    Anđelković, Katarina; Pevec, Andrej; Grubišić, Sonja; Turel, Iztok; Čobeljić, Božidar; Milenković, Milica R.; Keškić, Tanja; Radanović, Dušanka

    2018-06-01

    The mixed chloride-azide [ZnL(N3)1.65Cl0.35] (1) and chloride-isocyanate [CdL(NCO)1.64Cl0.36] (2) complexes with the condensation product of 2-quinolinecarboxaldehyde and trimethylammonium acetohydrazide chloride (Girard's T reagent) (HLCl) have been prepared and characterized by X-ray crystallography. In complexes 1 and 2, Zn1 and Cd1 ions, respectively, are five-coordinated in a distorted square based pyramidal geometry with NNO set of donor atoms of deprotonated hydrazone ligand and two monodentate ligands N3- and/or N3- and Cl- in the case of 1 and OCN- and/or OCN- and Cl- in the case of 2. The structural parameters of 1 and 2 have been discussed in relation to those of previously reported M(II) complexes with the same hydrazone ligand. Density functional theory calculations have been employed to study the interaction between the Zn2+ and Cd2+ ions and ligands. High affinity of ligands towards the Zn2+ and Cd2+ ions are predicted for both complexes.

  3. [3 + 2]-Cycloadditions of nitrile ylides after photoactivation of vinyl azides under flow conditions

    Directory of Open Access Journals (Sweden)

    Stephan Cludius-Brandt

    2013-08-01

    Full Text Available The photodenitrogenation of vinyl azides to 2H-azirines by using a photoflow reactor is reported and compared with thermal formation of 2H-azirines. Photochemically, the ring of the 2H-azirines was opened to yield the nitrile ylides, which underwent a [3 + 2]-cycloaddition with 1,3-dipolarophiles. When diisopropyl azodicarboxylate serves as the dipolarophile, 1,3,4-triazoles become directly accessible starting from the corresponding vinyl azide.

  4. Facile synthesis of 2,5-disubstituted thiazoles from terminal alkynes, sulfonyl azides, and thionoesters.

    Science.gov (United States)

    Miura, Tomoya; Funakoshi, Yuuta; Fujimoto, Yoshikazu; Nakahashi, Junki; Murakami, Masahiro

    2015-05-15

    A sequential procedure for the synthesis of 2,5-disubstituted thiazoles from terminal alkynes, sulfonyl azides, and thionoesters is reported. A copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with thionoesters in the presence of a rhodium(II) catalyst. The resulting 3-sulfonyl-4-thiazolines subsequently aromatize into the corresponding 2,5-disubstituted thiazoles by elimination of the sulfonyl group.

  5. Structural Determinants of Alkyne Reactivity in Copper-Catalyzed Azide-Alkyne Cycloadditions

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang

    2016-12-01

    Full Text Available This work represents our initial effort in identifying azide/alkyne pairs for optimal reactivity in copper-catalyzed azide-alkyne cycloaddition (CuAAC reactions. In previous works, we have identified chelating azides, in particular 2-picolyl azide, as “privileged” azide substrates with high CuAAC reactivity. In the current work, two types of alkynes are shown to undergo rapid CuAAC reactions under both copper(II- (via an induction period and copper(I-catalyzed conditions. The first type of the alkynes bears relatively acidic ethynyl C-H bonds, while the second type contains an N-(triazolylmethylpropargylic moiety that produces a self-accelerating effect. The rankings of reactivity under both copper(II- and copper(I-catalyzed conditions are provided. The observations on how other reaction parameters such as accelerating ligand, reducing agent, or identity of azide alter the relative reactivity of alkynes are described and, to the best of our ability, explained.

  6. Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

    Science.gov (United States)

    Wentrup, Curt

    2017-03-08

    Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N 2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N 2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

  7. Anion-exchange enrichment and spectrophotometric determination of uranium in sea-water

    International Nuclear Information System (INIS)

    Kuroda, Rokuro; Oguma, Koichi; Mukai, Noriko; Iwamoto, Masatoshi

    1987-01-01

    A method is proposed for the determination of uranium in sea-water. The uranium is strongly sorbed on a strongly basic anion-exchange resin (Cl - form) from acidified sea-water containing sodium azide (0.3M) and is easily eluted with 1M hydrochloric acid. Uranium in the effluent can be determined spectrophotometrically with Arsenazo III. The combined method allows easy and selective determination of uranium in sea-water without using a sophisticated adsorbent. The overall recovery and precision are satisfactory at the 3 μg/1. level. (author)

  8. 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.

  9. Metal-Anion Pairing at Oxide/Water Interfaces: Theoretical and Experimental Investigations from the Nanoscale to the Macroscale

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Heather [The Ohio State Univ., Columbus, OH (United States)

    2016-11-14

    We combine the use of several techniques including bulk adsorption experiments, X-ray absorption, infrared, total internal reflection Raman, and vibrational sum frequencygeneration (XAS, IR, TIR-Raman, VSFG) spectroscopies, and molecular modeling to investigate ion adsorption at mineral surfaces. XAS and TIR-Raman provides data on how the metal binds to the surface (e.g., monodentate, bidentate), IR provides data on bulk anion adsorption at mineral surfaces from aqueous solutions, and VSFG provides surface specific data on anion adsorption at the mineral surface as well as impact of adsorbed metal-anion pairs on water structure at the mineral surface. Molecular modeling is used to guide spectroscopic data interpretation by providing information on water structure around ions in solution and the structure of metal-anion complexes in aqueous solutions. In addition, molecular modeling is used to provide insight into water structure at mineral surfaces, the surface sites involved in ion adsorption, and the distribution of ion pairs between aqueous solution and the mineral surface. Our studies have focused on systems involving alkaline earth metal (Mg2+, Ca2+, Sr2+, Ba2+) and heavy metal (Co2+, Cd2+) cations. The anions we have selected for studyinclude Cl-, NO3-, ClO4-, SO42-, SeO32-, and SeO42-. Ion adsorption and the potential formation ofternary complexes on silica (quartz, amorphous silica), alumina (corundum and gibbsite), and ferric iron oxides (goethite and hematite) are under investigation.

  10. Copper-catalyzed azide alkyne cycloaddition polymer networks

    Science.gov (United States)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  11. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  12. Efficiency and effectiveness of gamma rays and sodium azide in Sesbania cannabina Poir

    International Nuclear Information System (INIS)

    Kumar, G.; Srivastava, N.

    2013-01-01

    Mutagenic effectiveness and efficiency is an important factor for the selection of a mutagen for a mutation breeding program. Mutagenic effectiveness is a measure of the frequency of mutations induced by a unit mutagen dose, while mutagenic efficiency is a measure of the proportion of mutations in relation to undesirable changes such as lethality, sterility, meiotic aberrations etc. The present study envisages the mutagenic effectiveness and efficiency of individual and combined treatments of chemical and physical mutagens i.e. sodium azide (individual), gamma rays (individual) and sodium azide + gamma ray (combined). For the individual treatment of sodium azide, the seeds of the Sesbania cannabina variety ND-1 were treated with 0.5% solution of sodium azide (SA) for four different time durations, i.e. 3, 5, 7, and 9 h, and for the individual treatment of gamma rays, dry and healthy seeds were treated with 20, 40, 60, and 80 Kr doses of gamma rays. For the combined treatment, the seeds were exposed to four different doses of gamma rays (20, 40, 60, and 80 Kr) and after irradiation seeds were treated with 0.5% solution of sodium azide for 3 h. After treatment, seeds subjected to individual and combined treatment were sown in randomized block design to raise the M 1 generation and a study was conducted on germination percentage, survival percentage, pollen fertility percentage, and chromosomal aberrations at different doses of the individual and combined treatments. (author)

  13. Effects of mutagen application of sodium azide and gamma radiation in rice seeds

    International Nuclear Information System (INIS)

    Guimaraes, E.P.

    1980-01-01

    Effects of mutagen application of sodium azide and gamma radiation in rice seeds. Upland rice seeds, variety Dourado Precoce, were treated with gamma-rays and sodium azide(SA). Biological effects of these treatments were studied in the M 1 and M 2 generations. Survival number, seedling height, plant fertility and chlorophyill mutation frequencies based on mutations per 100 M 1 panicles and mutants per 100 M 2 seedlings were analysed. Among these characters, plant fertility was the most sensitive for mutagen treatments, and higher doses of gamma-rays or higher concentrations of sodium azide reduced significantly fertility of M 1 plants. The same effect as increase of concentration of sodium azide was observed when the acidity of buffer solution was increased, or when seeds were pre-treated in distilled water. The maximum chlorophyll mutation frequencies were obtained in sodium azide treatments: 40.74% in the M 1 panicles and 10.67% in the M 2 seedlings, in comparison with the maximum frequenies in gamma-irradiation of 10.39% in the M 1 panicles and 1.73% in the M 2 seedlings. (Author) [pt

  14. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    International Nuclear Information System (INIS)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC 5 H 4 ) 3 U(thf), serves as a one- or two-electron reducing agent towards azides, RN 3 . These reactions produce either the uranium(IV) azide, (MeC 5 H 4 ) 3 UN 3 , or uranium(V) imides, (MeC 5 H 4 ) 3 UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me 3 XN 3 , the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph 3 XN 3 , the azide is produced when X = C or Sn. For Ph 3-x CH 3 N 3 , the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC 6 H 4 N 3 , only the imides are produced. The magnetic properties of uranium diimides, [(MeC 5 H 4 ) 3 U] 2 (μ-NRN), were investigated. Several uranium(III) amines, (MeC 5 H 4 ) 3 U(NH 2 R), were produced from (MeC 5 H 4 ) 3 U(thf) and RNH 2 , and NH 3 was found to be a better ligand towards (MeC 5 H 4 ) 3 U than is PMe 3

  15. Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer.

    Science.gov (United States)

    Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2016-09-28

    Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.

  16. Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

    Science.gov (United States)

    Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

    2018-04-01

    Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

  17. ANIONIC SYNTHESIS OF A "CLICKABLE" MIDDLE-CHAIN AZIDEFUNCTIONALIZED POLYSTYRENE AND ITS APPLICATION IN SHAPE AMPHIPHILES

    Institute of Scientific and Technical Information of China (English)

    Kan Yue; Jinlin He; Chang Liu; Mingjun Huang; Xue-Hui Dong; Kai Guo; Peihong Ni

    2013-01-01

    "Click chemistry" is,by definition,a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis.This paper reports the synthesis of a "clickable" middle-chain azide-functionalized polystyrene (mPS-N3) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS).The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide.Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography.The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential "click" strategy.The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS).The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls,resulting in an amphiphilic shape amphiphile,mPS-DPOSS.This synthetic approach is highly efficient and modular.It demonstrates the "click" philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile "clickable" motif in polymer science for the precise synthesis of complex macromolecules.

  18. Synthesis of radiolabelled aryl azides from diazonium salts: experimental and computational results permit the identification of the preferred mechanism.

    Science.gov (United States)

    Joshi, Sameer M; de Cózar, Abel; Gómez-Vallejo, Vanessa; Koziorowski, Jacek; Llop, Jordi; Cossío, Fernando P

    2015-05-28

    Experimental and computational studies on the formation of aryl azides from the corresponding diazonium salts support a stepwise mechanism via acyclic zwitterionic intermediates. The low energy barriers associated with both transition structures are compatible with very fast and efficient processes, thus making this method suitable for the chemical synthesis of radiolabelled aryl azides.

  19. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Li-Wei [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan (China); Luo, Tzuoo-Tsair [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Wang, Chih-Min [Department of Bioscience and Biotechnology, National Taiwan Ocean University, Keelung 202, Taiwan (China); Lee, Gene-Hsiang; Peng, Shie-Ming [Department of Chemistry, National Taiwan University, Taipei 107, Taiwan (China); Liu, Yen-Hsiang [Department of Chemistry, Fu Jen Catholic University, New Taipei City 242, Taiwan (China); Lee, Sheng-Long [Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan (China); Lu, Kuang-Lieh [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China)

    2016-07-15

    A Cd(II)–organic framework {[Cd_2(tpim)_4(SO_4)(H_2O)_2]·(SO_4)·21H_2O}{sub n} (1) was synthesized by reacting CdSO{sub 4}·8/3H{sub 2}O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim){sub 2}]{sub n} chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO{sub 4}{sup 2−} anions, i.e., bridging SO{sub 4}{sup 2−} and free SO{sub 4}{sup 2−} anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN{sup −} anions, both the bridging and free SO{sub 4}{sup 2−} anions in 1 were completely exchanged by SCN{sup −} ligands to form a 1D species [Cd(tpim){sub 2}(SCN){sub 2}] (1A), in which the SCN{sup –} moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N{sub 3}{sup −} anions in aqueous solution, the bridging SO{sub 4}{sup 2−} moieties remained intact, and only the free guest SO{sub 4}{sup 2−} were replaced by N{sub 3}{sup −} anions. The gas adsorption behavior of the activated compound 1 was also investigated. - Highlights: • An interesting anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework is reported. • The sulfate-incorporated 2D layer compound exhibits very different anion exchange behavior with respect to SCN{sup −} and N{sub 3}{sup −}. • Both the bridging and free SO{sub 4}{sup 2−} anions in the 2D structure were completely exchanged by SCN{sup −} ligands, resulting in the formation of a 1D species. However, in the case of N{sub 3}{sup −} anions, only the free guest SO{sub 4}{sup 2−} in the structure was replaced.

  20. Synthesis of positron labeled photoactive compounds: 18F labeled aryl azides for positron labeling of biochemical molecules

    International Nuclear Information System (INIS)

    Hashizume, Kazunari; Hashimoto, Naota; Miyake, Yoshihiro

    1995-01-01

    The authors have prepared various [ 18 F] fluorine labeled aryl azides as a novel photoactive compounds suitable for positron labeling of biochemical molecules. The introduction of fluorine substituents to aryl azides can be expected to have dramatic effects on their nature and reactivity toward photolysis. Positron labeled reagents for labeling proteins or peptides have recently attracted considerable attention due to their wide applicability in biochemistry and positron emission tomography (PET). Various labeled azide compounds are often used in biochemistry for radiolabeling biological molecules by photolysis, but there have been no reports on the preparation or use of fluorine-18 labeled azides. The authors now report a novel synthesis of 18 F-labeled aryl azides which will have wide application in the biochemistry and nuclear medicine as a means for 18 F-fluorine labeling for proteins, peptides, and nucleic acids. 2 tabs

  1. Anionic surface binders

    OpenAIRE

    Aljaž-Rožič Mateja; Hočevar Nežka

    2004-01-01

    The MELAMIN Chemical Factory in Kočevje manufactures synthetic resins and binders for the paper industry. Binders based on AKD (alkyl ketene dimer) are produced which are used for binding paper and cardboard in the range of neutral and partially basic pH. Cationic and, lately, anionic binders are mostly used for the bulk binding of paper and board. The possibility of using AKD binders on paper or board surfaces is presented. In this case partially cationic AKD binders may be applied. When opt...

  2. 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

  3. Alkylating efficiency of sodium azide on pod yield, nut size and ...

    African Journals Online (AJOL)

    Mutation has been utilised to improve growth and yield of many food crops, but only little effort has been made to ascertain the nutritional advantages in such improved crops. The present study evaluates the alkylating efficiency of sodium azide of different concentrations on pod yield, nut size and nutritional composition of ...

  4. Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

    Science.gov (United States)

    Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

    2011-01-04

    Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

  5. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun

    2017-02-15

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

  6. Biological and genetic effects of combined treatments of sodium azide, gamma rays and EMS in barley

    International Nuclear Information System (INIS)

    Cheng, X.Y.; Gao, M.W.

    1988-01-01

    Dry seeds of diploid barley were subjected to mutagenic treatments of sodium azide, gamma rays and EMS alone or in combination. Damage (reduction in seedling height, plant height and fertility), the frequency of chimeras in the M1 generation, and the frequency of chlorophyll-deficient mutations as well as morphological mutations in the M2 generation induced by combined treatments were greater than those by either of the single treatments. Synergistic increase in the frequency of chimeras, chlorphyll-deficient mutations and morphological mutations were observed in both sodium azide post-irradiation treatments and pre-EMS treatments; interaction among the mutagens in the treatment combinations on M1 damage was generally subtractive. An 8- to 16-hr soaking period of irradiated seeds in distilled water prior to sodium azide treatment significantly increased chlorophyll mutation frequency, as compared to that from the non-soaking treatment. Damage and frequency of chimeras, chlorophyll mutations and morphological mutations were consistently reduced by the soaking treatment in sodium azide plus EMS treatments. (author)

  7. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones

    Directory of Open Access Journals (Sweden)

    Farhan R. Bou-Hamdan

    2011-08-01

    Full Text Available Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  8. Azidoperfluoroalkanes: Synthesis and Application in Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

    Czech Academy of Sciences Publication Activity Database

    Blastik, Zsófia E.; Voltrová, Svatava; Matoušek, V.; Jurásek, Bronislav; Manley, David W.; Klepetářová, Blanka; Beier, Petr

    2017-01-01

    Roč. 56, č. 1 (2017), s. 346-349 ISSN 1433-7851 EU Projects: European Commission(XE) 607787 - FLUOR21 Institutional support: RVO:61388963 Keywords : azides * click reactions * fluorine * perfluoroalkanes * triazoles Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 11.994, year: 2016 http://onlinelibrary.wiley.com/doi/10.1002/anie.201609715/full

  9. In situ generation of the Ohira-Bestmann Reagent from stable sulfonyl azide

    DEFF Research Database (Denmark)

    Jepsen, Tue Heesgaard; Kristensen, Jesper Langgaard

    2014-01-01

    We report an improved method for in situ generation of the Ohira-Bestmann reagent. Using the recently reported bench stable imidazole-1-sulfonyl azide as diazotransfer reagent, this new method represents a safe and scalable approach for the transformation of aldehydes into terminal alkynes...

  10. Continuous flow hydrogenation of nitroarenes, azides and alkenes using maghemite-Pd nanocomposites

    Science.gov (United States)

    Maghemite-supported ultra-fine Pd (1-2 nm) nanoparticles, prepared by a simple co-precipitation method, find application in the catalytic continuous flow hydrogenation of nitroarenes, azides, and alkenes wherein they play an important role in reduction of various functional group...

  11. Copper on Chitosan: A Recyclable Heterogeneous Catalyst for Azide-alkyne Cycloaddition Reactions in Water

    Science.gov (United States)

    Copper sulfate is immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with copper sulfate; the ensuing catalyst has been utilized for the azide-alkyne cycloaddition in aqueous media and it can be recycled and reused many time without loosing it...

  12. 49 CFR 173.182 - Barium azide-50 percent or more water wet.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Barium azide-50 percent or more water wet. 173.182 Section 173.182 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS... Class 1 and Class 7 § 173.182 Barium azide—50 percent or more water wet. Barium azide—50 percent or more...

  13. C,N-Chelated Organotin(IV) Azides: Synthesis, Structure and Use within the Click Chemistry.

    Czech Academy of Sciences Publication Activity Database

    Švec, P.; Bartoš, K.; Růžičková, Z.; Cuřínová, Petra; Dušek, L.; Turek, J.; de Proft, F.; Růžička, A.

    2016-01-01

    Roč. 40, č. 7 (2016), s. 5808-5817 ISSN 1144-0546 Grant - others:FWO(BE) 12T6615N Institutional support: RVO:67985858 Keywords : organotin(IV)azides * click chemistry * chelation Subject RIV: CC - Organic Chemistry Impact factor: 3.269, year: 2016

  14. Manganese(II), iron(II), and mixed-metal metal-organic frameworks based on chains with mixed carboxylate and azide bridges: magnetic coupling and slow relaxation.

    Science.gov (United States)

    Wang, Yan-Qin; Yue, Qi; Qi, Yan; Wang, Kun; Sun, Qian; Gao, En-Qing

    2013-04-15

    Mn(II) and Fe(II) compounds derived from azide and the zwitterionic 1-carboxylatomethylpyridinium-4-carboxylate ligand are isomorphous three-dimensional metal-organic frameworks (MOFs) with the sra net, in which the metal ions are connected into anionic chains by mixed (μ-1,1-azide)bis(μ-carboxylate) triple bridges and the chains are cross-linked by the cationic backbones of the zwitterionic ligands. The Mn(II) MOFs display typical one-dimensional antiferromagnetic behavior. In contrast, with one more d electron per metal center, the Fe(II) counterpart shows intrachain ferromagnetic interactions and slow relaxation of magnetization attributable to the single-chain components. The activation energies for magnetization reversal in the infinite- and finite-chain regimes are Δτ1 = 154 K and Δτ2 = 124 K, respectively. Taking advantage of the isomorphism between the Mn(II) and Fe(II) MOFs, we have prepared a series of mixed-metal Mn(II)(1-x)Fe(II)(x) MOFs with x = 0.41, 0.63, and 0.76, which intrinsically feature random isotropic/anisotropic sites and competing antiferromagnetic-ferromagnetic interactions. The materials show a gradual antiferromagnetic-to-ferromagnetic evolution in overall behaviors as the Fe(II) content increases, and the Fe-rich materials show complex relaxation processes that may arise for mixed SCM and spin-glass mechanisms. A general trend is that the activation energy and the blocking temperature increase with the Fe(II) content, emphasizing the importance of anisotropy for slow relaxation of magnetization.

  15. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  16. 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 ...

  17. Comparison of physiological and genetic effects of gamma radiation and sodium azide on two rice (Oryza sativa, L.) genotypes

    International Nuclear Information System (INIS)

    Faracco, A.L.A.

    1990-01-01

    The sensitivity of both genotypes (Oryzica 1 and Strain 30036) to gamma rays and sodium azide is studied. Doses of gamma-rays and concentrations of sodium azide were chosen so as to produce around 20%-25% height reduction in these genotypes. Emergence, survival and fertility were the physiological effects on M 1 generation analysed after the final treatment. The number of chlorophyll mutations and the number of seedling mutants were counted in M 2 generation. Taking into consideration, specially M 1 generation sterility, it was concluded that for the two genotypes studied, sodium azide presented a greater mutagen effect. (M.A.C.)

  18. Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

    KAUST Repository

    Johansson, Johan R.

    2011-04-01

    An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

  19. Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium

    International Nuclear Information System (INIS)

    Benaud, Olivier; Berthet, Jean-Claude; Thuery, Pierre; Ephritikhine, Michel

    2011-01-01

    In contrast to the neutral macrocycle [UN* 2 (N,C)] (1) [N* = N(SiMe 3 ) 3 ; N,C = CH 2 SiMe 2 N-(SiMe 3 )] which was quite inert toward I 2 , the anionic bismetallacycle [NaUN*(N,C) 2 ] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me 3 Si)NSiMe 2 CH 2 CH 2 SiMe 2 N(SiMe 3 )] resulting from C-C coupling of the two CH 2 groups, and [NaUN*(N,O) 2 ] (3) [N,O = OC(=CH 2 )SiMe 2 N(SiMe 3 )], which is devoid of any U-C bond, was oxidized into the UV bismetallacycle [Na{UN*(N,O) 2 }2(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN 3 or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN* 2 (N,C)(N 3 )] [M = Na, 7a or Na(15-crown-5), 7b], M[UN* 2 (N,C)(CN)] [M = NEt 4 , 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N 3 ) 2 ] [M = Na, 9a or Na(THF)4, 9b], [NEt 4 ][UN*(N,N)(CN) 2 ] (10), M[UN*(N,O) 2 (N 3 )] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O) 2 (CN)] [M = NEt 4 , 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral UV complex [U(N{SiMe 3 }-SiMe 2 C{CHI}O) 2 I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined. (authors)

  20. Environmental Friendly Azide-Alkyne Cycloaddition Reaction of Azides, Alkynes, and Organic Halides or Epoxides in Water: Efficient "Click" Synthesis of 1,2,3-Triazole Derivatives by Cu Catalyst

    Institute of Scientific and Technical Information of China (English)

    刘建明; 刘慕文; 岳园园; 姚美焕; 卓克垒

    2012-01-01

    An efficient click synthesis of 1,2,3-triazole derivatives from benzyl halides or alkyl halides, epoxides, terminal alkynes, and sodium azides in the presence of copper salts and relative benzimidazole salts have been developed. This procedure eliminates the need to handle potentially organic azides, which are generated in situ. A broad spec- trum of substrates can participate in the process effectively to produce the desired products in good yields.

  1. Direct C–H Azidation of Calix[4]arene as a Novel Method to Access Meta Substituted Derivatives

    Czech Academy of Sciences Publication Activity Database

    Stejskal, F.; Eigner, V.; Dvořáková, H.; Cuřínová, Petra; Lhoták, P.

    2015-01-01

    Roč. 56, č. 39 (2015), s. 5357-5361 ISSN 0040-4039 Institutional support: RVO:67985858 Keywords : calixarene * azidation * regionselectivity Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

  2. Synthesis of novel bis(perfluorophenyl azides) coupling agents: Evaluation of their performance by crosslinking of poly(ethylene oxide)

    KAUST Repository

    Mehenni, Hakim; Bakr, Osman

    2011-01-01

    Novel bis(perfluorophenyl azides) coupling agents, containing spacer arms from ethylene or ethylene glycol subunits, were successfully synthesized. Nitrenes photogenerated from these novel bis(PFPA) coupling agents were applied successfully

  3. 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.

  4. Consecutive hydrazino-Ugi-azide reactions: synthesis of acylhydrazines bearing 1,5-disubstituted tetrazoles

    Directory of Open Access Journals (Sweden)

    Angélica de Fátima S. Barreto

    2017-12-01

    Full Text Available Isocyanide-based multicomponent reactions (IMCRs allow the construction of relatively complex molecules through a one-pot synthesis. The combination of IMCRs in a consecutive or sequential fashion further extends the complexity of the molecules obtained. Herein, we report the efficient application of this approach to the synthesis of acylhydrazines bearing 1,5-disubstituted tetrazoles. Our strategy was accomplished in only three steps: first, a one-pot hydrazino-Ugi-azide four-component reaction; second a hydrazinolysis and finally an additional hydrazino-Ugi-azide reaction. This sequence provides the title compounds in moderate to excellent yields. The products synthesized herein contain functional groups within their structures that can be easily modified to obtain new acylhydrazino 1,5-disubstituted tetrazoles.

  5. Experimental evidence for the involvement of dinuclear alkynylcopper(I) complexes in alkyne-azide chemistry.

    Science.gov (United States)

    Buckley, Benjamin R; Dann, Sandra E; Heaney, Harry

    2010-06-01

    Dinuclear alkynylcopper(I) ladderane complexes are prepared by a robust and simple protocol involving the reduction of Cu(2)(OH)(3)OAc or Cu(OAc)(2) by easily oxidised alcohols in the presence of terminal alkynes; they function as efficient catalysts in copper-catalysed alkyne-azide cycloaddition reactions as predicted by the Ahlquist-Fokin calculations. The same copper(I) catalysts are formed during reactions by using the Sharpless-Fokin protocol. The experimental results also provide evidence that sodium ascorbate functions as a base to deprotonate terminal alkynes and additionally give a convincing alternative explanation for the fact that the Cu(I)-catalysed reactions of certain 1,3-diazides with phenylacetylene give bis(triazoles) as the major products. The same dinuclear alkynylcopper(I) complexes also function as catalysts in cycloaddition reactions of azides with 1-iodoalkynes.

  6. Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution.

    Science.gov (United States)

    Xue, Jiadan; Luk, Hoi Ling; Eswaran, S V; Hadad, Christopher M; Platz, Matthew S

    2012-06-07

    The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).

  7. Gamma ray and sodium azide induced heterophylly of Bhindi and Clusterbean

    International Nuclear Information System (INIS)

    Khaleel Basha, S.; Gopala Rao, P.

    1988-01-01

    Gamma rays (35, 45 Krad) and sodium azide (100, 200 ppm) and their combinations caused heterophylly in Bhindi (Hibiscus esculentus) and Clusterbean (Cyamopsis tetragonoloba). Changes like notching of leaf at the tip region, reduction of secondary and tertiary veins, formation of 2,4 leaflets, reduction of leaf lobes and change of shape were noticed. More changes were observed at higher doses of the mutagens. (author). 12 refs

  8. Functionalization of Graphene Nanoplatelets Using Sugar Azide for Graphene/Epoxy Nanocomposites

    Science.gov (United States)

    2014-06-20

    supercapacitor electrode . Nanotechnology, 22, 295202(2011). doi:10.1088/0957-4484/22/29/295202 20. Leinonen H, Pettersson M, Lajunen M, Water-soluble...Azide for Graphene/Epoxy Nanocomposites Saswata Bose1, Lawrence T. Drzal 1* Dept of Chemical Engineering and Materials Science Composite Materials ...ORGANIZATION NAME(S) AND ADDRESS(ES) Dept of Chemical Engineering and Materials Science,Composite Materials and Structures Center,2100 Engineering

  9. Synthesis of polynorbornene with pendant moiety bearing azide and terminal alkyne groups

    Institute of Scientific and Technical Information of China (English)

    Ze Zhang; Zhi Wei Peng; Kun Zeng Fan

    2011-01-01

    A powerful approach to the synthesis of an unprecedented polynorbornene with pendant moiety bearing azide and terminal alkyne groups is developed. Two key intermediates, namely, 3-azido-5-(2-(trimethylsilyl)ethynyl) benzyl alcohol and 4-(4-aza-tricyclo [5.2.1.02.6]dec-8-en-4-yl) benzoic acid, were optimally synthesized for convergent synthesis of the corresponding monomer.

  10. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Directory of Open Access Journals (Sweden)

    Karl Hemming

    2014-10-01

    Full Text Available The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs, pyrrolo[1,2,5]benzothiadiazepines (PBTDs, and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  11. A practical and azide-free synthetic approach to oseltamivir from diethyl D-tartrate.

    Science.gov (United States)

    Weng, Jiang; Li, Yong-Bo; Wang, Rui-Bin; Li, Feng-Quan; Liu, Can; Chan, Albert S C; Lu, Gui

    2010-05-07

    A short and practical synthesis of oseltamivir was accomplished in 11 steps from inexpensive and abundant diethyl D-tartrate starting material. This azide-free route featured an asymmetric aza-Henry reaction and a domino nitro-Michael/Horner-Wadsworth-Emmons (HWE) reaction as the key steps to construct the relevant cyclohexene ring of the product, which provided an economical and practical alternative for the synthesis of oseltamivir.

  12. Pressure-accelerated azide-alkyne cycloaddition: micro capillary versus autoclave reactor performance.

    Science.gov (United States)

    Borukhova, Svetlana; Seeger, Andreas D; Noël, Timothy; Wang, Qi; Busch, Markus; Hessel, Volker

    2015-02-01

    Pressure effects on regioselectivity and yield of cycloaddition reactions have been shown to exist. Nevertheless, high pressure synthetic applications with subsequent benefits in the production of natural products are limited by the general availability of the equipment. In addition, the virtues and limitations of microflow equipment under standard conditions are well established. Herein, we apply novel-process-window (NPWs) principles, such as intensification of intrinsic kinetics of a reaction using high temperature, pressure, and concentration, on azide-alkyne cycloaddition towards synthesis of Rufinamide precursor. We applied three main activation methods (i.e., uncatalyzed batch, uncatalyzed flow, and catalyzed flow) on uncatalyzed and catalyzed azide-alkyne cycloaddition. We compare the performance of two reactors, a specialized autoclave batch reactor for high-pressure operation up to 1800 bar and a capillary flow reactor (up to 400 bar). A differentiated and comprehensive picture is given for the two reactors and the three methods of activation. Reaction speedup and consequent increases in space-time yields is achieved, while the process window for favorable operation to selectively produce Rufinamide precursor in good yields is widened. The best conditions thus determined are applied to several azide-alkyne cycloadditions to widen the scope of the presented methodology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

    Directory of Open Access Journals (Sweden)

    Stefanie Wolfram

    2014-10-01

    Full Text Available Molecular probes are widely used tools in chemical biology that allow tracing of bioactive metabolites and selective labeling of proteins and other biomacromolecules. A common structural motif for such probes consists of a reporter that can be attached by copper(I-catalyzed 1,2,3-triazole formation between terminal alkynes and azides to a reactive headgroup. Here we introduce the synthesis and application of the new thiazole-based, azide-tagged reporter 4-(3-azidopropoxy-5-(4-bromophenyl-2-(pyridin-2-ylthiazole for fluorescence, UV and mass spectrometry (MS detection. This small fluorescent reporter bears a bromine functionalization facilitating the automated data mining of electrospray ionization MS runs by monitoring for its characteristic isotope signature. We demonstrate the universal utility of the reporter for the detection of an alkyne-modified small molecule by LC–MS and for the visualization of a model protein by in-gel fluorescence. The novel probe advantageously compares with commercially available azide-modified fluorophores and a brominated one. The ease of synthesis, small size, stability, and the universal detection possibilities make it an ideal reporter for activity-based protein profiling and functional metabolic profiling.

  14. Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt

    2013-07-01

    Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  15. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  16. 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

  17. Introduction of sample tubes with sodium azide as a preservative for ethyl glucuronide in urine.

    Science.gov (United States)

    Luginbühl, Marc; Weinmann, Wolfgang; Al-Ahmad, Ali

    2017-09-01

    Ethyl glucuronide (EtG) is a direct alcohol marker, which is widely used for clinical and forensic applications, mainly for abstinence control. However, the instability of EtG in urine against bacterial degradation or the post-collectional synthesis of EtG in contaminated samples may cause false interpretation of EtG results in urine samples. This study evaluates the potential of sodium azide in tubes used for urine collection to hinder degradation of ethyl glucuronide by bacterial metabolism taking place during growth of bacterial colonies. The tubes are part of a commercial oral fluid collection device. The sampling system was tested with different gram-positive and gram-negative bacterial species previously observed in urinary tract infections, such as Escherichia coli, Staphylococcus aureus, Enterecoccus faecalis, Staphylococcus epidermidis, Klebsiella pneumoniae, Enterobacter cloacae, and Pseudomonas aeruginosa. Inhibition of bacterial growth by sodium azide, resulting in lower numbers of colony forming units compared to control samples, was observed for all tested bacterial species. To test the prevention of EtG degradation by the predominant pathogen in urinary tract infection, sterile-filtered urine and deficient medium were spiked with EtG, and inoculated with E. coli prior to incubation for 4 days at 37 °C in tubes with and without sodium azide. Samples were collected every 24 hours, during four consecutive days, whereby the colony forming units (CFU) were counted on Columbia blood agar plates, and EtG was analyzed by LC-MS/MS. As expected, EtG degradation was observed when standard polypropylene tubes were used for the storage of contaminated samples. However, urine specimens collected in sodium azide tubes showed no or very limited bacterial growth and no EtG degradation. As a conclusion, sodium azide is useful to reduce bacterial growth of gram-negative and gram-positive bacteria. It inhibits the degradation of EtG by E. coli and can be used for

  18. Characterization of the anion sensitive ATPase in intact vacuoles of Kalanchoe diagremontiana

    Energy Technology Data Exchange (ETDEWEB)

    Kobza, J.; Uribe, E.G.

    1986-04-01

    A method for the isolation of intact vacuoles from K. daigremontiana was developed which produced high yields of relatively pure vacuoles as determined by marker enzyme contamination. Upon isolation, the vacuoles were stabilized by the inclusion of 5% (w/v) ficoll. Enzyme activity was insensitive to vanadate and azide but was strongly inhibited by DCCD. Enzyme activity was strictly dependent on the inclusion of Mg/sup 2 +/ and was stimulated by anions as depicted by the series, NO/sub 3//sup -/ < Br/sup -/ < SO/sub 4//sup -/ < HCO/sub 3//sup -/ < Cl/sup -/. It was found that in intact vacuoles the ATPase activity was stimulated by phosphate to a level equivalent to that found with the chloride. The enzyme exhibited Michaelis-Menten kinetics with a Km for Mg-ATP complex of 0.51 mM.

  19. Synthesis, solid-state structure, and bonding analysis of a homoleptic beryllium azide

    International Nuclear Information System (INIS)

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Roemer, Beate; Blaeser, Dieter; Woelper, Christoph; Jansen, Georg; Schulz, Stephan

    2017-01-01

    [Ph 4 P] 2 [Be(N 3 ) 4 ] (1) and [PNP] 2 [Be(N 3 ) 4 ] (2; PNP=Ph 3 PNPPh 3 ) were synthesized by reacting Be(N 3 ) 2 with [Ph 4 P]N 3 and [PNP]N 3 . Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N 3 ) 4 ] 2- were investigated by quantum-chemical calculations (NPA, ELF, LOL). (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Azide- and Alkyne-Functionalised α- and β3-Amino Acids

    DEFF Research Database (Denmark)

    Sminia, T.J.; Pedersen, Daniel Sejer

    2012-01-01

    The synthesis and full characterisation of bifunctional β -amino acids that have side chains functionalised with terminal azides (S)-4 and (R)-4 or acetylenes 5 and 6 is reported for the first time. The building blocks incorporate a turn-inducing β -segment and a side chain that can...... be functionalised further, for example, through copper-catalysed Huisgen cycloaddition. Moreover, the corresponding α-amino acids 1 and 3 have been synthesised and characterised. All amino acid building blocks were of high optical purity as demonstrated by derivatisation and subsequent NMR analysis....

  1. Synthesis, Solid-State Structure, and Bonding Analysis of a Homoleptic Beryllium Azide.

    Science.gov (United States)

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Römer, Beate; Bläser, Dieter; Wölper, Christoph; Jansen, Georg; Schulz, Stephan

    2017-07-10

    [Ph 4 P] 2 [Be(N 3 ) 4 ] (1) and [PNP] 2 [Be(N 3 ) 4 ] (2; PNP=Ph 3 PNPPh 3 ) were synthesized by reacting Be(N 3 ) 2 with [Ph 4 P]N 3 and [PNP]N 3 . Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N 3 ) 4 ] 2- were investigated by quantum-chemical calculations (NPA, ELF, LOL). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Allylic azides as potential building blocks for the synthesis of nitrogenated compounds

    Directory of Open Access Journals (Sweden)

    Sá Marcus M.

    2003-01-01

    Full Text Available The synthetic potential of multifunctional allylic azides and imines in attempted intramolecular cyclizations to nitrogen-containing heterocycles was investigated. Tandem Staudinger/aza-Wittig reaction of (E-3-aryl-2-(azidomethylpropenoates with triphenylphosphine and aldehydes yielded N-allylic imines in good yield. The (E-stereochemistry of C=C and C=N bonds was assigned based on NOESY experiments. AlCl3 mediated formation of 3-carbomethoxyquinoline from methyl (E-2-(azidomethyl-3-phenylpropenoate is also described.

  3. 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.

  4. Ionic liquids comprising heteraromatic anions

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, William F.; Brennecke, Joan F.; Maginn, Edward J.; Mindrup, Elaine; Gurkan, Burcu; Price, Erica; Goodrich, Brett

    2018-04-24

    Some embodiments described herein relate to ionic liquids comprising an anion of a heteraromatic compound such as optionally substituted pyrrolide, optionally substituted pyrazolide, optionally substituted indolide, optionally substituted phospholide, or optionally substituted imidazolide. Methods and devices for gas separation or gas absorption related to these ionic liquids are also described herein.

  5. 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.

  6. IMPROVING OF ANION EXCHANGERES REGENERATION

    Directory of Open Access Journals (Sweden)

    Muzher M. Ibrahim

    2013-05-01

    Full Text Available Inthis study, Different basis [NaOH and KOH] of variable concentration are usedto reactivate Anion exchangers employing different schemes .The Laboratoryresults showed large improvement in efficiency of these exchangers ( i.eoperating time was increased from 12 to 42 hours .The results of this work showed that the environmentalload (waste water can be reduced greatly when using the proposed regenerationscheme .

  7. Quantum mechanics of toroidal anions

    International Nuclear Information System (INIS)

    Afanas'ev, G.N.

    1990-01-01

    We consider a toroidal solenoid with an electric charge attached to it. It turns out that statistical properties of the wave function describing interacting toroidal anions depend on both their relative position and orientation. The influence of the particular gauge choice on the exchange properties of the wave function is studied. 30 refs.; 6 figs

  8. 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.

  9. 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.

  10. 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.

  11. Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

    Science.gov (United States)

    Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

    2001-10-22

    The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

  12. Copper-Catalyzed Sulfonyl Azide-Alkyne Cycloaddition Reactions: Simultaneous Generation and Trapping of Copper-Triazoles and -Ketenimines for the Synthesis of Triazolopyrimidines.

    Science.gov (United States)

    Nallagangula, Madhu; Namitharan, Kayambu

    2017-07-07

    First simultaneous generation and utilization of both copper-triazole and -ketenimine intermediates in copper-catalyzed sulfonyl azide-alkyne cycloaddition reactions is achieved for the one-pot synthesis of triazolopyrimidines via a novel copper-catalyzed multicomponent cascade of sulfonyl azides, alkynes, and azirines. Significantly, the reaction proceeds under very mild conditions in good yields.

  13. Theoretical investigation of some high-performance novel amine azide propellants

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Debasis [Computational Fluid Dynamics Research Corp., Huntsville, AL 35805 (United States); Raman, Sumathi [Department of Chemistry, Oakwood College, 2000 Adventist Blvd., Huntsville, AL 35896 (United States)

    2007-08-15

    Monomethylhydrazine (MMH) is currently the most widely used hypergolic propellant, due to its high performance and low ignition delay. However, its toxicity is a major concern. The present work aims at developing high-performance hypergolic fuels that are based on tertiary amine azide functionality. A number of potential amine azide candidates have been proposed, and some of their physical and chemical properties have been computed using state-of-the-art molecular modeling techniques. Gas-phase heats of formation have been calculated using the CBS-QB3 method, and the first-principle COSMO-RS method has been used to compute heats of vaporization and vapor pressures. A density correlation, based on molecular-volume calculation, has been established to predict the densities of the candidate molecules. Finally, the liquid-phase heats of formation and densities have been used to predict the specific and density impulses of the proposed candidate molecules. The results show that many of the molecules proposed here have much higher density impulse than that of MMH, and may be considered for experimental studies. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  14. Rice mutants obtained through sodium azide (NaN3) treatment

    International Nuclear Information System (INIS)

    Silva, E.F.; Ando, A.; Tulmann Neto, A.

    2001-01-01

    The successful utilization of sodium azide to generate genetic variability in plant breeding has been reported in barley, rice, and other crops. Rice seeds of 'Dourado Precoce', Brazilian upland cultivar, were treated with 5x10 -3 M of sodium azide, prepared in buffer solution of pH 3,0, for 8 hours at laboratory temperature. Ten short culm mutant lines were selected in the M 2 , M 3 and M 4 generations. In the M 5 generation, the mutant lines were evaluated for flowering and maturing cycles, tiller number per plant, plant height, panicle number per m 2 , panicle length, fertility of panicle, weight of 1.000 grains, productivity, percentage of intact grains after milling, width and thickness of peeled and polished grains and length/width grain ratio. The experiment was conducted in the Centro Experimental of Instituto Agronomico, Campinas, Sao Paulo, Brazil, during the period of 1993/94, utilizing randomized block design with four replications. Each experimental plot consisted of five rows of four meters in length, 50 cm between rows, with 75 seeds sown per meter. The cultivar 'IAC 201' and the original Dourado Precoce were planted as checks. All observations were made on the three central rows of each experimental plot. The data was analysed by the SANEST statistical program and the mean values were discriminated by the Tukey's test at the level 5% of probability

  15. Ratiometric Fluorescence Azide-Alkyne Cycloaddition for Live Mammalian Cell Imaging.

    Science.gov (United States)

    Fu, Hongxia; Li, Yanru; Sun, Lingbo; He, Pan; Duan, Xinrui

    2015-11-17

    Click chemistry with metabolic labeling has been widely used for selectively imaging biomacromolecules in cells. The first example of azide-alkyne cycloaddition for ratiometric fluorescent imaging of live cells is reported. The precursor of the azido fluorophore (cresyl violet) has a fluorescence emission peak at 620 nm. The electron-rich nitrogen of the azido group blue-shifts the emission peak to 566 nm. When the click reaction occurs, an emission peak appears at 620 nm due to the lower electronic density of the newly formed triazole ring, which allows us to ratiometrically record fluorescence signals. This emission shift was applied to ratiometric imaging of propargylcholine- and dibenzocyclooctyne-labeled human breast cancer cells MCF-7 under laser confocal microscopy. Two typical triazole compounds were isolated for photophysical parameter measurements. The emission spectra presented a fluorescence emission peak around 620 nm for both click products. The results further confirmed the emission wavelength change was the result of azide-alkyne cycloaddition reaction. Since nearly all biomolecules can be metabolically labeled by reported alkyne-functionalized derivatives of native metabolites, our method can be readily applied to image these biomacromolecules.

  16. 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

  17. 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.

  18. 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.

  19. 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...

  20. Development of a general methodology for labelling peptide-morpholino oligonucleotide conjugates using alkyne-azide click chemistry.

    Science.gov (United States)

    Shabanpoor, Fazel; Gait, Michael J

    2013-11-11

    We describe a general methodology for fluorescent labelling of peptide conjugates of phosphorodiamidate morpholino oligonucleotides (PMOs) by alkyne functionalization of peptides, subsequent conjugation to PMOs and labelling with a fluorescent compound (Cy5-azide). Two peptide-PMO (PPMO) examples are shown. No detrimental effect of such labelled PMOs was seen in a biological assay.

  1. Solid-phase synthesis of NH-1,2,3-triazoles using 4,4′- bismethoxybenzhydryl azide

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil O'Hanlon; Le Quement, Sebastian Thordal; Nielsen, Thomas Eiland

    2014-01-01

    Readily available 4,4′-bismethoxybenzhydryl azide was found to be a useful building block for the synthesis of NH-1,2,3-triazoles through copper(I)-catalyzed cycloaddition reactions with solid-supported terminal alkynes, followed by acid-mediated deprotection. Peptide-containing NH-1,2,3-triazole...

  2. Target and identify: triazene linker helps identify azidation sites of labelled proteins via click and cleave strategy.

    Science.gov (United States)

    Lohse, Jonas; Schindl, Alexandra; Danda, Natasha; Williams, Chris P; Kramer, Karl; Kuster, Bernhard; Witte, Martin D; Médard, Guillaume

    2017-10-31

    A method for identifying probe modification of proteins via tandem mass spectrometry was developed. Azide bearing molecules are immobilized on functionalised sepharose beads via copper catalysed Huisgen-type click chemistry and selectively released under acidic conditions by chemical cleavage of the triazene linkage. We applied this method to identify the modification site of targeted-diazotransfer on BirA.

  3. Determination of gold osmium and ruthenium through iodine-azide reaction in presence of 2- or 6- mercaptopurine

    International Nuclear Information System (INIS)

    Matusiewicz, H.; Kurzawa, Z.

    1978-01-01

    The composition of osmium and ruthenium complexes with 6-mercaptopurine has been determined. The sensitivity of the method was enhanced due to a proper choice of the optimal time of the formation of these complexes and the time of equilibrium attainment in the presence of excess of azide. Also the gold complex with 2-mercaptopurine was investigated. (author)

  4. 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

  5. Azide-Alkyne Huisgen [3+2] Cycloaddition Using CuO Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hyunjoon Song

    2012-11-01

    Full Text Available Recent developments in the synthesis of CuO nanoparticles (NPs and their application to the [3+2] cycloaddition of azides with terminal alkynes are reviewed. With respect to the importance of click chemistry, CuO hollow NPs, CuO hollow NPs on acetylene black, water-soluble double-hydrophilic block copolymer (DHBC nanoreactors and ZnO–CuO hybrid NPs were synthesized. Non-conventional energy sources such as microwaves and ultrasound were also applied to these click reactions, and good catalytic activity with high regioselectivity was observed. CuO hollow NPs on acetylene black can be recycled nine times without any loss of activity, and water-soluble DHBC nanoreactors have been developed for an environmentally friendly process.

  6. Relative Performance of Alkynes in Copper-Catalyzed Azide-Alkyne Cycloaddition

    Science.gov (United States)

    Kislukhin, Alexander A.; Hong, Vu P.; Breitenkamp, Kurt E.; Finn, M.G.

    2013-01-01

    Copper-catalyzed azide–alkyne cycloaddition (CuAAC) has found numerous applications in a variety of fields. We report here only modest differences in the reactivity of various classes of terminal alkynes under typical bioconjugative and preparative organic conditions. Propargyl compounds represent an excellent combination of azide reactivity, ease of installation, and cost. Electronically activated propiolamides are slightly more reactive, at the expense of increased propensity for Michael addition. Certain alkynes, including tertiary propargyl carbamates, are not suitable for bioconjugation due to copper-induced fragmentation. A fluorogenic probe based on such reactivity is available in one step from rhodamine 110 and can be useful for optimization of CuAAC conditions. PMID:23566039

  7. Synthesis, solid-state structure, and bonding analysis of a homoleptic beryllium azide

    Energy Technology Data Exchange (ETDEWEB)

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Roemer, Beate; Blaeser, Dieter; Woelper, Christoph; Jansen, Georg; Schulz, Stephan [Faculty of Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), Duisburg-Essen Univ., Essen (Germany)

    2017-07-10

    [Ph{sub 4}P]{sub 2}[Be(N{sub 3}){sub 4}] (1) and [PNP]{sub 2}[Be(N{sub 3}){sub 4}] (2; PNP=Ph{sub 3}PNPPh{sub 3}) were synthesized by reacting Be(N{sub 3}){sub 2} with [Ph{sub 4}P]N{sub 3} and [PNP]N{sub 3}. Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N{sub 3}){sub 4}]{sup 2-} were investigated by quantum-chemical calculations (NPA, ELF, LOL). (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

    Science.gov (United States)

    Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

    2017-11-27

    Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

    KAUST Repository

    Hou, Duenren

    2010-11-01

    A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

  10. Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

    KAUST Repository

    Hou, Duenren; Kuan, Tingchun; Li, YuKai; Lee, Richmond; Huang, Kuo-Wei

    2010-01-01

    A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

  11. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan

    2003-01-01

    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  12. Exploring the flexible chemistry of 4-fluoro-3-nitrophenyl azide for biomolecule immobilization and bioconjugation.

    Science.gov (United States)

    Kumar, Saroj; Kumar, Dileep; Ahirwar, Rajesh; Nahar, Pradip

    2016-10-01

    Bioconjugation and functionalization of polymer surfaces are two major tasks in materials chemistry which are accomplished using a variety of coupling agents. Immobilization of biomolecules onto polymer surfaces and the construction of bioconjugates are essential requirements of many biochemical assays and chemical syntheses. Different linkers with a variety of functional groups are used for these purposes. Among them, the benzophenones, aryldiazirines, and arylazides represent the most commonly used photolinker to produce the desired chemical linkage upon their photo-irradiation. In this review, we describe the versatile applications of 4-fluoro-3-nitrophenyl azide, one of the oldest photolinkers used for photoaffinity labeling in the late 1960s. Surprisingly, this photolinker, historically known as 1-fluoro-2-nitro-4-azidobenzene (FNAB), has remained unexplored for a long time because of apprehension that FNAB forms ring-expanded dehydroazepine as a major product and hence cannot activate an inert polymer. The first evidence of photochemical activation of an inert surface by FNAB through nitrene insertion reaction was reported in 2001, and the FNAB-activated surface was found to conjugate a biomolecule without any catalyst, reagent, or modification. FNAB has distinct advantages over perfluorophenyl azide derivatives, which are contemporary nitrene-generating photolinkers, because of its simple, single-step preparation and ease of thermochemical and photochemical reactions with versatile polymers and biomolecules. Covering these aspects, the present review highlights the flexible chemistry of FNAB and its applications in the field of surface engineering, immobilization of biomolecules such as antibodies, enzymes, cells, carbohydrates, oligonucleotides, and DNA aptamers, and rapid diagnostics. Graphical Abstract An overview of the FNAB-engineered activated polymer surfaces for covalent ligation of versatile biomolecules.

  13. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion

    Energy Technology Data Exchange (ETDEWEB)

    Transue, Wesley J.; Velian, Alexandra; Nava, Matthew; Martin-Drumel, Marie-Aline; Womack, Caroline C.; Jiang, Jun; Hou, Gao-Lei; Wang, Xue-Bin; McCarthy, Michael C.; Field, Robert W.; Cummins, Christopher C.

    2016-06-01

    Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been characterized by molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH = 25.5 kcal/mol and ΔS = ₋2.43 e.u., and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3- , for which structural data have been obtained in a single-crystal Xray diffraction study. Negative ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3- has been assessed using nucleus-independent chemical shift (NICS), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) methods.

  14. Environmental behavior of inorganic anions

    International Nuclear Information System (INIS)

    Garland, T.R.; Cataldo, D.A.; Fellows, R.J.; Wildung, R.E.

    1987-01-01

    Recent efforts have addressed two aspects of anion behavior in the soil/plant system. The first involves evaluation of the gaseous component of the terrestrial iodine cycle in soils and plants. Field analyses of 129 I in soils and vegetation adjacent to a fuels reprocessing facility, which was idle for 10 years prior to the study, indicated that there may be a significant gaseous component to the terrestrial iodine cycle. Soil substrates, including a silt-sand, organic forest soil, quartz sand, and a sterilized soil, were amended with radioiodide, and the rates and quality of the volatile components evaluated

  15. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    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 for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  16. The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: Implications for the enzyme mechanism‡

    Science.gov (United States)

    Ogura, Hiroshi; Evans, John P.; Peng, Dungeng; Satterlee, James D.; de Montellano, Paul R. Ortiz; Mar, Gerd N. La

    2009-01-01

    The active site electronic structure of the azide complex of substrate-bound human heme oxygenase-1, (hHO) has been investigated by 1H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. 2D 1H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts, that places the lone iron π-spin in the dxz orbital, rather than the dyz orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy and magnetic susceptibilities argues for a low-spin, (dxy)2(dyz,dxz)3, ground state in both azide and cyanide complexes. The switch from singly-occupied dyz for the cyanide to dxz for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide π-plane in the latter complex, which is ∼90° in-plane rotated from that of the imidazole π-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicate that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 → Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed. PMID:19243105

  17. The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: implications for the enzyme mechanism.

    Science.gov (United States)

    Ogura, Hiroshi; Evans, John P; Peng, Dungeng; Satterlee, James D; Ortiz de Montellano, Paul R; La Mar, Gerd N

    2009-04-14

    The active site electronic structure of the azide complex of substrate-bound human heme oxygenase 1 (hHO) has been investigated by (1)H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. Two-dimensional (1)H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts that places the lone iron pi-spin in the d(xz) orbital, rather than the d(yz) orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy, and magnetic susceptibilities argues for a low-spin, (d(xy))(2)(d(yz),d(xz))(3), ground state in both azide and cyanide complexes. The switch from singly occupied d(yz) for the cyanide to d(xz) for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide pi-plane in the latter complex, which is approximately 90 degrees in-plane rotated from that of the imidazole pi-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicates that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 --> Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed.

  18. Gamma ray, EMS and sodium azide induced effectiveness and efficiency of chlorophyll mutations in basmati rice (Oryza sativa L.)

    International Nuclear Information System (INIS)

    Singh, Sanjeev; Singh, J.; Singh, R.K.

    2001-01-01

    The effectiveness and efficiency of gamma ray, EMS, sodium azide alone or in combination in relation to chlorophyll mutations in two varieties of Basmati rice (Oryza sativa L.) in M 2 generation were studied. The chlorophyll mutations were induced by all the doses of mutagens alone or in combination relatively at a fair frequency in both the varieties in M 2 generation. In general, it was found that combination treatments of gamma rays and EMS were observed to be more efficient in Taraori Basmati, while EMS alone and combination treatment of gamma rays and EMS were more efficient in Pusa Basmati 1 on sterility and growth injury basis both. Sodium azide at 0.5 mM was found as the most effective dose in both Taraori Basmati and Pusa Basmati 1 cultivars. (author)

  19. Detection of Alkynes via Click Chemistry with a Brominated Coumarin Azide by Simultaneous Fluorescence and Isotopic Signatures in Mass Spectrometry.

    Science.gov (United States)

    Yang, Lihua; Chumsae, Chris; Kaplan, Jenifer B; Moulton, Kevin Ryan; Wang, Dongdong; Lee, David H; Zhou, Zhaohui Sunny

    2017-09-20

    Alkynes are a key component of click chemistry and used for a wide variety of applications including bioconjugation, selective tagging of protein modifications, and labeling of metabolites and drug targets. However, challenges still exist for detecting alkynes because most 1,2,3-triazole products from alkynes and azides do not possess distinct intrinsic properties that can be used for their facile detection by either fluorescence or mass spectrometry. To address this critical need, a novel brominated coumarin azide was used to tag alkynes and detect alkyne-conjugated biomolecules. This tag has several useful properties: first, it is fluorogenic and the click-chemistry products are highly fluorescent and quantifiable; second, its distinct isotopic pattern facilitates identification by mass spectrometry; and third, its click-chemistry products form a unique pair of reporter ions upon fragmentation that can be used for the quick screening of data. Using a monoclonal antibody conjugated with alkynes, a general workflow has been developed and examined comprehensively.

  20. [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination.

    Science.gov (United States)

    Kanchupalli, Vinaykumar; Katukojvala, Sreenivas

    2018-05-04

    A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. The effects of sodium azide on seed germination and seedling growth of chili pepper (Capsicum annum L. cv. Landung)

    Science.gov (United States)

    Yafizham; Herwibawa, B.

    2018-01-01

    This study was aimed to determine the effects of sodium azide on the performance of chili pepper. Dry seeds from pure lines of chili pepper cv. Landung were used in this experiment. Each set containing 50 seeds was placed in nylon fishner bags, washed in flowing water and soaked in distilled water for four hours. After soaking, four sets of seeds were dabbed dry with tissue paper and were treated for two hours at 30 0C in appropriate solution of 0, 0.10, 0.20, 0.40, 0.80, 1.60 mM sodium azide with phosphate buffer at pH 3. After treatment, the seeds were germinated in plastic boxes containing sterilized sand and kept under laboratory condition by supplied with water everyday. The seeds for M1 germination percentage, seedling height, plant height and number of leaves were recorded 30 days and 60 days after treatment, respectively. Seeds which radicle emerged were considered germinated, the seedling and plant height were measured from the tip of primary root to the base of the first leaf pair, and the number of leaves were counted for only fully expanded leaves. A completely randomized block design in four replicates was used throughout the experiment. Data obtained were analysed for range, mean, standard of deviation, and percent of control using Microsoft Office Excel 2007 software. It was concluded that different doses of sodium azide influenced the performances of chili pepper cv. Landung. Very low doses of sodium azide (0-1.60 mM) might be used to study the improvement of chili pepper diversity.

  3. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  4. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi

    2013-01-01

    Full Text Available A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields.

  5. In situ generation of the Ohira-Bestmann reagent from stable sulfonyl azide: scalable synthesis of alkynes from aldehydes.

    Science.gov (United States)

    Jepsen, Tue Heesgaard; Kristensen, Jesper Langgaard

    2014-10-03

    We report an improved method for in situ generation of the Ohira-Bestmann reagent. Using the recently reported bench-stable imidazole-1-sulfonyl azide as diazotransfer reagent, this new method represents a scalable and convenient approach for the transformation of aldehydes into terminal alkynes. The method features an easier workup compared to the existing in situ protocol due to increased aqueous solubility of waste products.

  6. Synthesis of novel bis(perfluorophenyl azides) coupling agents: Evaluation of their performance by crosslinking of poly(ethylene oxide)

    KAUST Repository

    Mehenni, Hakim

    2011-11-01

    Novel bis(perfluorophenyl azides) coupling agents, containing spacer arms from ethylene or ethylene glycol subunits, were successfully synthesized. Nitrenes photogenerated from these novel bis(PFPA) coupling agents were applied successfully to the cross-linking of poly(ethylene oxide) (PEO10,000) in either aqueous medium or at the solid state, thus, we demonstrated the potential of these bis(PFPA) molecules as promising coupling agents in surface engineering. © 2011 Elsevier Ltd. All rights reserved.

  7. Sequential continuous flow processes for the oxidation of amines and azides by using HOF·MeCN.

    Science.gov (United States)

    McPake, Christopher B; Murray, Christopher B; Sandford, Graham

    2012-02-13

    The generation and use of the highly potent oxidising agent HOF·MeCN in a controlled single continuous flow process is described. Oxidations of amines and azides to corresponding nitrated systems by using fluorine gas, water and acetonitrile by sequential gas-liquid/liquid-liquid continuous flow procedures are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

    International Nuclear Information System (INIS)

    Kennedy, Zachary C.; Barrett, Christopher A.; Warner, Marvin G.

    2017-01-01

    Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here in this paper we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g –1 ) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.

  9. Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles.

    Science.gov (United States)

    Kennedy, Zachary C; Barrett, Christopher A; Warner, Marvin G

    2017-03-21

    Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g -1 ) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Improved metal-adhesive polymers from copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Accurso, Adrian A; Delaney, Mac; O'Brien, Jeff; Kim, Hyonny; Iovine, Peter M; Díaz Díaz, David; Finn, M G

    2014-08-18

    Electrically conductive adhesive polymers offer many potential advantages relative to Sn-Pb solders, including reduced toxicity, low cost, low processing temperatures, and the ability to make application-specific formulations. Polymers generated from the copper(I)-catalyzed cycloaddition (CuAAC) reaction between multivalent azides and alkynes have previously been identified as strong metal-binding adhesives. Herein we demonstrate that the performance of these materials can be remarkably improved by the incorporation of a flexibility-inducing difunctionalized component and a tertiary amine additive in optimized concentrations. The best formulations were identified by means of rapid adhesion testing of a library of potential candidates by using a custom-built instrument and validated in an American Society for Testing and Materials (ASTM)-standard lap-shear test. Characteristic phase transitions were identified by differential scanning calorimetry (DSC) for adhesives with and without the additives as a function of curing temperature. The incorporation of flexible components was found to more than double the strength of the adhesive. Moreover, the adhesive was made electrically conductive by the inclusion of 20 wt% silver-coated copper flakes and further improved in this regard by the incorporation of multiwalled carbon nanotubes in the formulation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation

    KAUST Repository

    Du, Naiying; Dal-Cin, Mauro M D; Pinnau, Ingo; Nicalek, Andrzej; Robertson, Gilles P.; Guiver, Michael D.

    2011-01-01

    Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O 2/N 2 and CO 2/N 2 gas pairs, as well as for condensable gases, such as CO 2/CH 4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO 2 plasticization up to 20 atm pressure of pure CO 2 and CO 2/CH 4 mixtures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation

    KAUST Repository

    Du, Naiying

    2011-03-11

    Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O 2/N 2 and CO 2/N 2 gas pairs, as well as for condensable gases, such as CO 2/CH 4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO 2 plasticization up to 20 atm pressure of pure CO 2 and CO 2/CH 4 mixtures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Mutagenic effectiveness and efficiency of EMS, sodium azide and gamma radiation in chickpea (Cicer arietinum L.)

    International Nuclear Information System (INIS)

    Barshile, J.D.; Apparao, B.J.

    2006-01-01

    Mutagenic effectiveness and efficiency of Ethyl Methane Sulphonate (EMS), Sodium Azide (SA) and gamma radiation on two cultivars of chickpea (Cicer arietinum L), Vijay and Vishwas were evaluated by the biological damages caused by them in M 1 generation and on the basis of frequency of chlorophyll mutations produced in the M 2 generation. All mutagenic treatments of EMS, SA and gamma radiation decreased germination, seedling height, plant survival and pollen fertility in both the cultivars. The extent of effect was dose dependent. LD 50 values of mutagen were found to be helpful for planning experimental mutagenesis in chickpea. Frequency of chlorophyll mutations in M 2 generation was less in Vijay as compared to Vishwas. Mutagenic effectiveness is inversely proportional to the increasing concentrations/doses of mutagens in both the cultivars, except for gamma radiation treatments in the cultivar Vishwas. All three mutagens (except EMS in the Vijay and gamma radiation in the cultivar Vishwas) exhibited gradual decrease in mutagenic efficiency, with an increase in their concentration/dose. (author)

  19. 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 ...

  20. Synthesis, Spectroscopy, Theoretical, and Electrochemical Studies of Zn(II, Cd(II, and Hg(II Azide and Thiocyanate Complexes of a New Symmetric Schiff-Base Ligand

    Directory of Open Access Journals (Sweden)

    Morteza Montazerozohori

    2013-01-01

    Full Text Available Synthesis of zinc(II/cadmium(II/mercury(II thiocyanate and azide complexes of a new bidentate Schiff-base ligand (L with general formula of MLX2 (M = Zn(II, Cd(II, and Hg(II in ethanol solution at room temperature is reported. The ligand and metal complexes were characterized by using ultraviolet-visible (UV-visible, Fourier transform infrared (FT-IR, 1H- and 13C-NMR spectroscopy and physical characterization, CHN analysis, and molar conductivity. 1H- and 13C-NMR spectra have been studied in DMSO-d6. The reasonable shifts of FT-IR and NMR spectral signals of the complexes with respect to the free ligand confirm well coordination of Schiff-base ligand and anions in an inner sphere coordination space. The conductivity measurements as well as spectral data indicated that the complexes are nonelectrolyte. Theoretical optimization on the structure of ligand and its complexes was performed at the Becke’s three-parameter hybrid functional (B3 with the nonlocal correlation of Lee-Yang-Parr (LYP level of theory with double-zeta valence (LANL2DZ basis set using GAUSSIAN 03 suite of program, and then some theoretical structural parameters such as bond lengths, bond angles, and torsion angles were obtained. Finally, electrochemical behavior of ligand and its complexes was investigated. Cyclic voltammograms of metal complexes showed considerable changes with respect to free ligand.

  1. 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.

  2. Biosensor Technology Reveals the Disruption of the Endothelial Barrier Function and the Subsequent Death of Blood Brain Barrier Endothelial Cells to Sodium Azide and Its Gaseous Products.

    Science.gov (United States)

    Kho, Dan T; Johnson, Rebecca H; O'Carroll, Simon J; Angel, Catherine E; Graham, E Scott

    2017-09-21

    Herein we demonstrate the sensitive nature of human blood-brain barrier (BBB) endothelial cells to sodium azide and its gaseous product. Sodium azide is known to be acutely cytotoxic at low millimolar concentrations, hence its use as a biological preservative (e.g., in antibodies). Loss of barrier integrity was noticed in experiments using Electric Cell-substrate Impedance Sensing (ECIS) biosensor technology, to measure endothelial barrier integrity continuously in real-time. Initially the effect of sodium azide was observed as an artefact where it was present in antibodies being employed in neutralisation experiments. This was confirmed where antibody clones that were azide-free did not mediate loss of barrier function. A delayed loss of barrier function in neighbouring wells implied the influence of a liberated gaseous product. ECIS technology demonstrated that the BBB endothelial cells had a lower level of direct sensitivity to sodium azide of ~3 µM. Evidence of gaseous toxicity was consistently observed at 30 µM and above, with disrupted barrier function and cell death in neighbouring wells. We highlight the ability of this cellular biosensor technology to reveal both the direct and gaseous toxicity mediated by sodium azide. The sensitivity and temporal dimension of ECIS technology was instrumental in these observations. These findings have substantial implications for the wide use of sodium azide in biological reagents, raising issues of their application in live-cell assays and with regard to the protection of the user. This research also has wider relevance highlighting the sensitivity of brain endothelial cells to a known mitochondrial disruptor. It is logical to hypothesise that BBB endothelial dysfunction due to mitochondrial dys-regulation could have an important but underappreciated role in a range of neurological diseases.

  3. Stereoselective Synthesis of(Z)-4-(2-Bromovinyl)benzenesulfonyl Azide and Its Synthetic Utility for the Transformation to(2)-N-[4-(2-Bromovinyl)benzenesulfonyl]imidates

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wensheng; KUANG Chunxiang; YANG Qing

    2009-01-01

    A novel method for the stereoselective synthesis of(Z)-4-(2-bromovinyl)benzenesulfonyl azide by simultaneous azidation and debrorninative decarboxylation of anti-2,3-dibromo-3-(4-chlorosulfonylphenyl)propanoic acid using NaN3 only was developed.Facile transformation of(Z)-4-(2-bromovinyl)benzenesulfonyl azide to(Z)-N-[4(2-bromovinyl)benzenesulfonyl]imidates was also achieved by Cu-catalyzed three-component coulping of (Z)-4-(2-bromovinyi)benzenesulfonyl azide,terminal alkynes and alcohols/phenols.

  4. Pressure induced polymorphism in ammonium azide (NH{sub 4}N{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Medvedev, S.A., E-mail: s.medvedev@mpic.de [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Institute fuer Anorganische und Analytische Chemie, Johannes Gutenberg-Universitaet, D-55099 Mainz (Germany); Eremets, M.I. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Evers, J.; Klapoetke, T.M. [Energetic Materials Research, Ludwig-Maximilian University Munich (LMU), Butenandtstrasse 5-13(D), D-81377 Munich (Germany); Palasyuk, T. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany); Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Trojan, I.A. [Max-Planck-Institute for Chemistry, Postfach 3060, D-55020 Mainz (Germany)

    2011-07-28

    Graphical abstract: Polymorph phase transition is observed in NH{sub 4}N{sub 3} at {approx}3 GPa by pressure dependent Raman studies. The strength of hydrogen bond appears to be modified at the phase transition as illustrated by dependence of N-H stretching frequency on pressure shown on figure. Highlights: {yields} Ammonium azide (NH{sub 4}N{sub 3}) studied at high pressures by Raman spectroscopy. {yields} Phase transition is observed at pressure {approx}3 GPa. {yields} Strength of hydrogen bond appears to be modified at the phase transition. {yields} NH{sub 4}N{sub 3} remain in molecular form up to pressures above 50 GPa. - Abstract: Pressure-dependent Raman spectroscopy studies reveal polymorph phase transition in simple molecular ionic crystal NH{sub 4}N{sub 3} at pressure {approx}3 GPa unobserved by recent abinitio evolutionary structure searches. Hydrogen bonding is spectroscopically evident in both low- and high-pressure phases. The strength of hydrogen bond appears to be modified at the phase transition: in the low-pressure phase NH{sub 4}N{sub 3} behaves as system with very strong hydrogen bonding whereas changes of spectra with pressure in the high-pressure phase are indicative of weak or medium-strength hydrogen bonds. The high pressure phase is most likely thermodynamically stable at least up to pressure {approx}55 GPa contradicting the abinitio studies predicting transformation of NH{sub 4}N{sub 3} to nonmolecular hydronitrogen solid at 36 GPa.

  5. Photografting of perfluoroalkanes onto polyethylene surfaces via azide/nitrene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Siegmann, Konstantin, E-mail: konstantin.siegmann@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Inauen, Jan, E-mail: jan.inauen@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Villamaina, Diego, E-mail: diego.villamaina@gmail.com [Visiting scientist at IMPE, Permanent address: Rapidplatz 3, CH-8953 Dietikon (Switzerland); Winkler, Martin, E-mail: martin.winkler@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland)

    2017-02-28

    The purpose of this study is to render polyethylene surfaces strongly and permanently hydrophobic. Polyethylene is a common plastic and, because of its inertness, difficult to graft. We chose polyethylene as example because of its ubiquity and model character. As graft chains linear perfluoroalkyl residues (−C{sub 4}F{sub 9}, −C{sub 6}F{sub 13}, −C{sub 8}F{sub 17} and −C{sub 10}F{sub 21}) were chosen, and photografting was selected as grafting method. Photolytically generated nitrenes can insert into carbon–hydrogen bonds and are therefore suited for binding to polyethylene. Hydrophobic photo reactive surface modifiers based on azide/nitrene chemistry are designed, synthesized in high yield and characterized. Four new molecules are described. Water contact angles exceeding 110° were achieved on grafted polyethylene. One problem is to demonstrate that the photografted surface modifiers are bound covalently to the polyethylene. Abrasion tests show that all new molecules, when photografted to polyethylene, have a higher abrasion resistance than a polyethylene surface coated with a long-chain perfluoroalkane. Relative abrasion resitances of 1.4, 2.0, 2.1 and 2.5 compared to the fluoroalkane coating were obtained for the four compounds. An abrasion model using ice is developed. Although all four compounds have the same λ{sub max} of 266 nm in acetonitrile solution, their molar extincition coefficients increase from 1.6·10{sup 4} to 2.2·10{sup 4} with increasing length of the fluorotelomer chain. Exitonic coupling of the chromophores of the surface modifiers is observed for specific molecules in the neat state. A linear correlation of water contact angle with fluorine surface content, as measured by photoelectron spectroscopy, in grafted polyethylene surfaces is established.

  6. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    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

  7. Synthesis and characterization of cyclic polystyrene using copper-catalyzed alkyne-azide cycloaddition coupling - evaluation of physical properties and optimization of cyclization conditions

    Science.gov (United States)

    Elupula, Ravinder

    . Whereas, anionically prepared A-PS had much higher reliance on the molecular weight changes for its glass transition temperature. However, in thin films, c-PS films have, within error, no confinement effect. In contrast, A-PS has seen large T g reduction with confinement. Ellipsometry analysis suggests that this invariance of the Tg-confinement effect in c-PS is a result of the weak perturbation to Tg near the free surface (i.e. the polymer-air interface). These weak perturbations are the result of the high packing efficiency of cyclic PS segments. The copper-catalyzed alkyne/azide cycloaddition (CuAAC) click reaction has been used to cyclize many linear polymers with complementary azide and alkyne end groups via unimolecular heterodifunctional approach. Cyclic polymers exhibit unique and potentially useful physical properties compared to their linear analogs, hence increasing interest in techniques for preparing this class of polymers. However, a general route for producing high purity cyclic polymers remained elusive. Prior to the discovery of "click" chemistry, it was difficult to produce highly pure cyclic polymers via the ring-closure approach, requiring extensive post-cyclization purification. However, even minor amounts of linear impurities can influence the physical properties of cyclic polymers. Thermal gradient interaction chromatography (TGIC) coupled with Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF MS) allows the fractionation of cyclic polymer samples and produce valuable data for determining both the quantity and identity of linear impurities. This understanding further enables us to optimize cyclization conditions towards the goal of and efficient, general methodology for producing highly pure cyclic polymers. To solve the ever-growing energy needs of the world and capture the renewable energy that is generated sporadically, we need to create devices that can store high amounts of energy and discharge power at

  8. 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.

  9. Metal-Free Poly-Cycloaddition of Activated Azide and Alkynes toward Multifunctional Polytriazoles: Aggregation-Induced Emission, Explosive Detection, Fluorescent Patterning, and Light Refraction.

    Science.gov (United States)

    Wu, Yongwei; He, Benzhao; Quan, Changyun; Zheng, Chao; Deng, Haiqin; Hu, Rongrong; Zhao, Zujin; Huang, Fei; Qin, Anjun; Tang, Ben Zhong

    2017-09-01

    The metal-free click polymerization (MFCP) of activated alkynes and azides or activated azide and alkynes have been developed into powerful techniques for the construction of polytriazoles without the obsession of metallic catalyst residues problem. However, the MFCP of activated azides and alkynes is rarely applied in preparation of functional polytriazoles. In this paper, soluble multifunctional polytriazoles (PIa and PIb) with high weight-average molecular weights (M w up to 32 000) are prepared via the developed metal-free poly-cycloaddition of activated azide and alkynes in high yields (up to 90%). The resultant PIa and PIb are thermally stable, and show aggregation-induced emission characteristics, enabling their aggregates to detect explosives with superamplification effect. Moreover, thanks to their containing aromatic rings and polar moieties, PIa and PIb exhibit high refractive indices. In addition, they can also be cross-linked upon UV irradiation to generate 2D fluorescent patterning due to their remaining azide groups and containing ester groups. Thus, these multifunctional polytriazoles are potentially applicable in the optoelectronic and sensing fields. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. AuBr3-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars.

    Science.gov (United States)

    Rajput, Jayashree; Hotha, Srinivas; Vangala, Madhuri

    2018-01-01

    Herein we report, for the first time, the successful anomeric azidation of per- O -acetylated and per- O -benzoylated sugars by catalytic amounts of oxophilic AuBr 3 in good to excellent yields. The method is applicable to a wide range of easily accessible per- O -acetylated and per- O -benzoylated sugars. While reaction with per- O -acetylated and per- O -benzoylated monosaccharides was complete within 1-3 h at room temperature, the per- O -benzoylated disaccharides needed 2-3 h of heating at 55 °C.

  11. Hydrothermal synthesis, characterization, and thermal properties of alumino silicate azide sodalite, Na8[AlSiO4]6(N3)2

    Science.gov (United States)

    Borhade, A. V.; Wakchaure, S. G.; Dholi, A. G.; Kshirsagar, T. A.

    2017-07-01

    First time we report the synthesis, structural characterization and thermal behavior of an unusual N3 - containing alumino-silicate sodalite mineral. Azide sodalite, Na8[AlSiO4]6(N3)2 has been synthesized under hydrothermal conditions at 433 K in steel lined Teflon autoclave. The structural and microstructural properties of azide sodalite mineral was characterized by various methods including FT-IR, XRD, SEM, TGA, and MAS NMR. Crystal structure have been refined by Rietveld method in P\\bar 43n space group, indicating that the N3 - sodalite has cubic in lattice. High temperature study was carried out to see the effect of thermal expansion on cell dimension ( a o) of azide sodalite. Thermal behavior of sodalite was also assessed by thermogravimetric method.

  12. Nonafluorobutanesulfonyl azide as a shelf-stable highly reactive oxidant for the copper-catalyzed synthesis of 1,3-diynes from terminal alkynes.

    Science.gov (United States)

    Suárez, José Ramón; Collado-Sanz, Daniel; Cárdenas, Diego J; Chiara, Jose Luis

    2015-01-16

    Nonafluorobutanesulfonyl azide is a highly efficient reagent for the copper-catalyzed coupling of terminal alkynes to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functional group compatibility. The reaction is extremely fast (<10 min), even at low temperature (−78 °C), and requires substoichiometric amounts of a simple copper(I) or copper(II) salt (2–5 mol %) and an organic base (0.6 mol %). A possible mechanistic pathway is briefly discussed on the basis of model DFT theoretical calculations. The quantitative assessment of the safety of use and shelf stability of nonafluorobutanesulfonyl azide has confirmed that this reagent is a superior and safe alternative to other electrophilic azide reagents in use today.

  13. 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

  14. 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

  15. Design and Synthesis of New Chacones Substituted with Azide/Triazole Groups and Analysis of Their Cytotoxicity Towards HeLa Cells

    Directory of Open Access Journals (Sweden)

    José A. F. P. Villar

    2012-08-01

    Full Text Available A series of new chalcones substituted with azide/triazole groups were designed and synthesized, and their cytotoxic activity was evaluated in vitro against the HeLa cell line. O-Alkylation, Claisen-Schmidt condensation and Cu(I-catalyzed cycloaddition of azides with terminal alkynes were applied in key steps. Fifteen compounds were tested against HeLa cells. Compound 8c was the most active molecule, with an IC50 value of 13.03 µM, similar to the value of cisplatin (7.37 µM.

  16. One-pot synthesis of 2,5-dihydropyrroles from terminal alkynes, azides, and propargylic alcohols by relay actions of copper, rhodium, and gold.

    Science.gov (United States)

    Miura, Tomoya; Tanaka, Takamasa; Matsumoto, Kohei; Murakami, Masahiro

    2014-12-01

    Relay actions of copper, rhodium, and gold formulate a one-pot multistep pathway, which directly gives 2,5-dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α-allenyl-α-amino ketones. Finally, a gold catalyst prompts 5-endo cyclization to produce 2,5-dihydropyrroles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Rhodium/Silver-Cocatalyzed Transannulation of N-Sulfonyl-1,2,3-triazoles with Vinyl Azides: Divergent Synthesis of Pyrroles and 2 H-Pyrazines.

    Science.gov (United States)

    Zhang, Lin; Sun, Ge; Bi, Xihe

    2016-11-07

    The first cyclization reaction between vinyl azides and N-sulfonyl-1,2,3-triazoles is reported. A Rh/Ag binary metal catalyst system proved to be necessary for the successful cyclization. By varying the structure of vinyl azides, such reaction allows the divergent synthesis of pyrroles and 2H-pyrazines. The cyclization reactions feature a broad substrate scope, good functional group tolerance, high reaction efficiency, and good to high product yields. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Effect of gamma radiations, ethyl methane sulfonate and sodium azide on the sennoside content in Cassia angustifolia

    International Nuclear Information System (INIS)

    Khalatkar, A.S.; Bhargava, Y.R.

    1987-01-01

    Cassia angustifolia commonly known as Tinnevelly Senna is an excellent source of sennosides. The leaflets of this plant constitute the principal raw material. To investigate the effect(s) of mutagenic treatments on phytochemical characteristics, the sand treated dry seeds of Senna were treated with different doses of gamma radiations, ethyl methane sulfonate and sodium azide for 18 hours duration at 24 ± 2°C. The treated population in M1 generation exhibited different degree of stimulation in growth. Other parameters were also affected by all the three mutagenic treatments. Seeds collected from M1 generation were sown and M2 plant progenies were raised. Morphological mutations with desirable characters were further investigated. Biochemical estimation of sennoside from the leaflets in vegetative and blooming phases was carried out. Of the three mutagens, 0.006% sodium azide yielded maximum sennoside in the vegetative phase; while, in the blooming phase, it was highest with 20 kR of gamma radiations. Seeds of these plant types hold promise for enhancing the sennoside yields per gram of tissue

  19. Development of an improved and early sowing potential variety of jute - binadeshipat-2 using chemical mutagen sodium azide

    International Nuclear Information System (INIS)

    Shamsuzzaman, K.M.; Saha, C.S.; Azad, M.A.K.

    2001-01-01

    Jute is the important agricultural and industrial resource of Bangladesh for earning foreign currency. Seeds of the widely cultivated variety, CVL-1 were treated with 4 mM to 20mM of sodium azide (NaN3). The treated seeds were grown in M1 to M10 generations. A single plant (selection number C-278) was selected from M2 segregating population on the basis of early sowing potential and late flowering. Ten fiber quality characters were tested and it was found that the fiber quality of the mutant had been improved. Hence, the mutagen sodium azide showed extra potentiality to induce fiber quality characters of jute. The strain C-278 was also tested through Preliminary, Advanced, Zonal Yield Trial and Farmers field trial at different locations of the jute growing area in Bangladesh. The field evaluation team of the National Seed Board (NSB) visited most of the trials and reported that at early sowing and overall performance of the strain C-278 was found best than that of the mother variety. Besides these the strain produced 7.5% and 20% higher fiber yield than the mother variety CVL-1 and a local cultivar, D-154, respectively. After evaluation of the Technical Committee of NSB recommended that the strain C-278 may be released as a variety. The National Seed Board released the strain C-278 as a National jute variety under the name Binadeshipat-2 for cultivation in Bangladesh

  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. 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...

  2. 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.

  3. 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

  4. The absorption of plutonium by anion resins

    Energy Technology Data Exchange (ETDEWEB)

    Durham, R. W.; Mills, R.

    1961-10-15

    Equilibrium experiments have shown Pu{sup +4} to be absorbed from nitric acid onto an anion resin as a complex anion Pu(NO{sub 3}){sub 6}{sup -2}. The amount of absorption is dependent on the plutonium and nitric acid concentrations in the equilibrium solution with a maximum at 7N to 8N HNO{sub 3}. A low cross-linked resin has a higher capacity and reaches equilibrium more rapidly than the normally supplied resin. Saturation capacity of one per cent cross-linked Nalcite SBR (Dowex 1), 50 -- 100 mesh, is 385 mg Pu/gram dry resin. (author)

  5. 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.

  6. 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

  7. 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)

  8. 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.

  9. Anion-conducting polymer, composition, and membrane

    Science.gov (United States)

    Pivovar, Bryan S [Los Alamos, NM; Thorn, David L [Los Alamos, NM

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  10. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.

    2005-01-01

    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  11. Topological ferrimagnetic behaviours of coordination polymers containing manganese(II) chains with mixed azide and carboxylate bridges and alternating F/AF/AF'/AF'/AF interactions.

    Science.gov (United States)

    Wang, Yan-Qin; Liu, Hou-Ting; Qi, Yan; Gao, En-Qing

    2014-08-21

    Two Mn(ii) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L(1)), {[Mn5(L(1))2(N3)8(OH)2]·12H2O}n () and {[Mn5(L(1))2(N3)8(H2O)2](ClO4)2·6H2O}n (), have been synthesized and characterized crystallographically and magnetically. and contain similar alternating chains constructed by azide and carboxylate bridges. The independent sets of bridges alternate in an ABCCB sequence between adjacent Mn(ii) ions: (EO-N3)2 double bridges (EO = end-on) (denoted as A), [(EO-N3)(OCO)2] triple bridges (denoted as B) and [(EO-N3)(OCO)] double bridges (denoted as C). The alternating chains are interlinked into 2D coordination networks by the tetrapyridinium spacers. Magnetic studies demonstrate that the magnetic coupling through the double EO azide bridges is ferromagnetic and that through mixed azide/carboxylate bridges is antiferromagnetic. The unprecedented F/AF/AF'/AF'/AF coupling sequence along the chain dictates an uncompensated ground spin state (S = 5/2 per Mn5 unit) and leads to one-dimensional topological ferrimagnetism, which features a minimum in the χT versus T plot.

  12. Determination of microgramme amounts of osmium and ruthenium based on inhibition of the iodine-azide reaction by their complexes with 6-mercaptopurine

    International Nuclear Information System (INIS)

    Matusiewicz, H.; Kurzawa, Z.

    1976-01-01

    A new kinetic method of the determination of microamounts of osmium and ruthenium has been developed. The reaction between sodum azide and iodine induced by 6-mercaptopurine (6-MP) was used for this purpose. Under suitable experimental conditions the induction coefficient of 6-MP amounts to 1750+-40. The formed complexes of the metals are stable in the medium containing an excess of azide ions and do not induce the iodine-azide reaction. The method consists in the determination of the 6-MP not bound to the metal. The amount of osmium or ruthenium is then determined from linear relations. Before the determination osmium and ruthenium must be separated from other cations and from each other by distillation as volatile tetroxides. The iodine-azide method is simple, sensitive and does not require any apparatus. The range of the determination is 0.1-5.0 μg in 5 cm 3 of the solution of Os(8) and 0.5-5.0 μg for Ru(8). The error of the determination is +-6.4% and +- 6.1% for osmium and ruthenium, respectively. The time of the determination is 30 minutes not taking into account 2-hour waiting time necessary for the formation of the complexes. (author)

  13. Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2010-01-01

    A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibility...

  14. Techniques in gas-phase thermolyses - Part 7. Direct surface participation in gas-phase Curie-point pyrolysis: The pyrolysis of phenyl azide

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars

    1986-01-01

    The possible direct participation of the hot reactor surface in the formation of pyrolysis products was elucidated through the pyrolytic decomposition of phenyl azide. It is demonstrated that the intermediate phenyl nitrene generated reacts with elemental carbon at the filament surface, leading...

  15. 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

  16. Solution NMR characterization of magnetic/electronic properties of azide and cyanide-inhibited substrate complexes of human heme oxygenase: implications for steric ligand tilt.

    Science.gov (United States)

    Peng, Dungeng; Ogura, Hiroshi; Ma, Li-Hua; Evans, John P; de Montellano, Paul R Ortiz; La Mar, Gerd N

    2013-04-01

    Solution 2D (1)H NMR was carried out on the azide-ligated substrate complex of human heme oxygenase, hHO, to provide information on the active site molecular structure, chromophore electronic/magnetic properties, and the distal H-bond network linked to the exogenous ligand by catalytically relevant oriented water molecules. While 2D NMR exhibited very similar patterns of two-dimensional nuclear Overhauser spectroscopy cross peaks of residues with substrate and among residues as the previously characterized cyanide complex, significant, broadly distributed chemical shift differences were observed for both labile and non-labile protons. The anisotropy and orientation of the paramagnetic susceptibility tensor, χ, were determined for both the azide and cyanide complexes. The most significant difference observed is the tilt of the major magnetic axes from the heme normal, which is only half as large for the azide than cyanide ligand, with each ligand tilted toward the catalytically cleaved α-meso position. The difference in chemical shifts is quantitatively correlated with differences in dipolar shifts in the respective complexes for all but the distal helix. The necessity of considering dipolar shifts, and hence determination of the orientation/anisotropy of χ, in comparing chemical shifts involving paramagnetic complexes, is emphasized. The analysis shows that the H-bond network cannot detect significant differences in H-bond acceptor properties of cyanide versus azide ligands. Lastly, significant retardation of distal helix labile proton exchange upon replacing cyanide with azide indicates that the dynamic stability of the distal helix is increased upon decreasing the steric interaction of the ligand with the distal helix. Copyright © 2013. Published by Elsevier Inc.

  17. 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

  18. 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.

  19. Two-Dimensional Infrared Study of Vibrational Coupling between Azide and Nitrile Reporters in a RNA Nucleoside.

    Science.gov (United States)

    Schmitz, Andrew J; Hogle, David G; Gai, Xin Sonia; Fenlon, Edward E; Brewer, Scott H; Tucker, Matthew J

    2016-09-08

    The vibrations in the azide, N3, asymmetric stretching region and nitrile, CN, symmetric stretching region of 2'-azido-5-cyano-2'-deoxyuridine (N3CNdU) are examined by two-dimensional infrared (2D IR) spectroscopy. At earlier waiting times, the 2D IR spectrum shows the presence of both vibrational transitions along the diagonal and off-diagonal cross peaks indicating vibrational coupling. The coupling strength is determined from the off-diagonal anharmonicity to be 66 cm(-1) for the intramolecular distance of ∼7.9 Å, based on a structural map generated for this model system. In addition, the frequency-frequency correlation decay is detected, monitoring the solvent dynamics around each individual probe position. Overall, these vibrational reporters can be utilized in tandem to simultaneously track global structural information and fast structural fluctuations.

  20. 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.

  1. 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%).

  2. Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s

    Science.gov (United States)

    Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun

    2018-01-01

    Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

  3. 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.

  4. Carboxymethyl glycoside lactone(CMGL) synthons:Scope of the method and preliminary results on step growth polymerization of α-azide-ω-alkyne glycomonomers

    Institute of Scientific and Technical Information of China (English)

    CHAMBERT; Stéphane; BERNARD; Julien; FLEURY; Etienne; QUENEAU; Yves

    2010-01-01

    Carboxymethyl glycoside lactones(CMGLs) are bicyclic synthons which open readily for accessing new types of pseudo-glycoconjugates,such as sugar-amino acid hybrids,neoglycolipids,pseudodisaccharides,and membrane imaging systems.After lactone opening,free OH-2 is available for further functionalization,leading to 1,2-bisfunctionalized derivatives.This strategy is illustrated herein with new polymerizable systems of the AB type bearing both azide and alkyne functions prepared from α or β gluco-CMGL synthons.After the reaction of lactones with propargylamine,an azido group was introduced by two different sequences leading to either the 2-manno-azido or the 6-gluco-azido products.The capability of these AB monomers to undergo step growth polymerization through copper(I) catalyzed alkyne-azide cycloaddition(CuAAC) and generate glycopolytriazoles was evidenced.

  5. 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.

  6. The pH dependence of the spectral and anion binding properties of iron containing superoxide dismutase from E. coli B

    International Nuclear Information System (INIS)

    Fee, J.A.; McClune, G.J.; Lees, A.C.; Zidovetzki, R.; Pecht, I.

    1981-01-01

    Examination of the optical and EPR properties of the ferric form of the iron containing superoxide dismutase from E.coli B, at pH values ranging from 4.5 to 10.9, has revealed two reversible structural transitions affecting the Fe 3+ ion. The apparent pKsub(a) values of these transitions are 5.1+-0.3 and 9.O+-0.3. The binding of azide has been studied over the pH range 4.5 to 10.7; the affinity of the Fe 3+ for N 3 - is independent of pH from 4.5 to approximately 7.5, after which the dissociation constant decreased by a factor of 10 per unit increase in pH. The apparent pKsub(a) which affects N 3 - binding to the iron is 8.6+-0.2. The association of N 3 - with the iron has been examined using the temperature-jump method at pH 7.4 and 9.3. The kinetics of ligand association were shown to conform to the minimal mechanism: P-Fe 3+ + N 3 - reversible K 1 N 3 - - P-Fe 3+ reversible K 2 P-Fe 3+ - N 3 - . K 1 was found to be essentially unaffected by pH whereas K 2 was much lower at pH 9.3 than at 7.4. The value of K 1 at pH 7.4 (100 M -1 ) corresponds very closely to that obtained for the inhibition constant of azide, 10mM. A scheme is presented in which N 3 - inhibits the iron containing dismutase by competing with O 2 - for an anion binding site near, but not on the Fe 3+ . (author)

  7. Facile solid-phase ruthenium assisted azide-alkyne cycloaddition (RuAAC) utilizing the Cp*RuCl(COD)-catalyst

    DEFF Research Database (Denmark)

    Engholm, Ebbe; sgz228, sgz228; Blixt, Klas Ola

    2017-01-01

    The ruthenium assisted azide-alkyne cycloaddition (RuAAC) reaction is a well-established method for the generation of 1,5- and 1,4,5-substituted 1,2,3-triazoles, which we have extended to the solid-phase synthesis of 1,2,3-triazole-peptides. The 1,2,3-triazole moieties were formed upon the reacti...

  8. Solvent effect on copper-catalyzed azide-alkyne cycloaddition (CuAAC): synthesis of novel triazolyl substituted quinolines as potential anticancer agents.

    Science.gov (United States)

    Ellanki, Amarender Reddy; Islam, Aminul; Rama, Veera Swamy; Pulipati, Ranga Prasad; Rambabu, D; Krishna, G Rama; Reddy, C Malla; Mukkanti, K; Vanaja, G R; Kalle, Arunasree M; Kumar, K Shiva; Pal, Manojit

    2012-05-15

    A regioselective route to novel mono triazolyl substituted quinolines has been developed via copper-catalyzed azide-alkyne cycloaddition (CuAAC) of 2,4-diazidoquinoline with terminal alkynes in DMF. The reaction provided bis triazolyl substituted quinolines when performed in water in the presence of Et(3)N. A number of the compounds synthesized showed promising anti-proliferative properties when tested in vitro especially against breast cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Facile synthesis of linear-dendritic cholesteryl-poly(epsilon-caprolactone)-b-(L-lysine)(G2) by thiol-ene and azide-alkyne "click" reactions

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Binder, W.H.; Tanner, S.

    2010-01-01

    The construction of a linear-dendritic block copolymer consisting of terminal cholesteryl moiety, poly(epsilon-caprolactone), and a second generation L-lysine dendron has been accomplished by the combination of copper(I) catalyzed azide-alkyne and UV-triggered thiol-ene "click" reactions. Ring-op...... and thiocholesterol. Near to quantitative functionalization of the intermediate and final products has been attained as confirmed by NMR spectroscopy and MALDI-TOF spectrometry....

  10. Synthesis, crystal structure, antimicrobial activity and electrochemistry study of chromium(III) and copper(II) complexes based on semicarbazone Schiff base and azide ligands

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Mahmoudi, F.

    2013-01-01

    Roč. 394, JAN (2013), s. 563-568 ISSN 0020-1693 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:68378271 Keywords : antimicrobial activity * azide ligand * metal complex * Schiff base ligand * X-ray structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.041, year: 2013

  11. 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

  12. Probes for anionic cell surface detection

    Science.gov (United States)

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  13. Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

    KAUST Repository

    Alkayal, Nazeeha

    2016-03-30

    Novel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).

  14. 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

  15. Site-Specific Antibody Labeling by Covalent Photoconjugation of Z Domains Functionalized for Alkyne-Azide Cycloaddition Reactions.

    Science.gov (United States)

    Perols, Anna; Arcos Famme, Melina; Eriksson Karlström, Amelie

    2015-11-01

    Antibodies are extensively used in research, diagnostics, and therapy, and for many applications the antibodies need to be labeled. Labeling is typically performed by using amine-reactive probes that target surface-exposed lysine residues, resulting in heterogeneously labeled antibodies. An alternative labeling strategy is based on the immunoglobulin G (IgG)-binding protein domain Z, which binds to the Fc region of IgG. Introducing the photoactivable amino acid benzoylphenylalanine (BPA) into the Z domain makes it possible for a covalent bond to be be formed between the Z domain and the antibody on UV irradiation, to produce a site-specifically labeled product. Z32 BPA was synthesized by solid-phase peptide synthesis and further functionalized to give alkyne-Z32 BPA and azide-Z32 BPA for Cu(I) -catalyzed cycloaddition, as well as DBCO-Z32 BPA for Cu-free strain-promoted cycloaddition. The Z32 BPA variants were conjugated to the human IgG1 antibody trastuzumab and site-specifically labeled with biotin or fluorescein. The fluorescently labeled trastuzumab showed specific staining of the membranes of HER2-expressing cells in immunofluorescence microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.)

  1. 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

  2. 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.

  3. Once upon Anion: A Tale of Photodetachment

    Science.gov (United States)

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  4. Adsorption of an anionic dispersant on lignite

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty

    2001-12-01

    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  5. Structures and properties of anionic clay minerals

    International Nuclear Information System (INIS)

    Koch, Chr. Bender

    1998-01-01

    The Moessbauer spectra of pyroaurite-sjoegrenite-type compounds (PTC) (layered anion exchangers) are discussed with reference to the crystal structure, cation order, and crystallite morphology. It is shown that cation-ordered layers are produced in the synthesis of carbonate and sulphate types of green rust. In contrast, synthetic and natural pyroaurite only occurs as disordered types. The redox chemistry of Fe(III) within the metal hydroxide layer is illustrated with examples of electrochemical oxidation and reversible reduction by boiling glycerol. The chemistry of iron in the interlayer is exemplified by the intercalation of Fe-cyanide complexes in hydrotalcite. This reaction may be used as a probe for the charge distribution in the interlayer

  6. Advanced polymer chemistry of organometallic anions

    International Nuclear Information System (INIS)

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.

    1997-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes

  7. Azide photochemistry for facile modification of graphitic surfaces: preparation of DNA-coated carbon nanotubes for biosensing

    International Nuclear Information System (INIS)

    Moghaddam, Minoo J; Yang Wenrong; Bojarski, Barbara; Gengenbach, Thomas R; Gao Mei; Zareie, Hadi; McCall, Maxine J

    2012-01-01

    A facile, two-step method for chemically attaching single-stranded DNA to graphitic surfaces, represented here by carbon nanotubes, is reported. In the first step, an azide-containing compound, N-5-azido-nitrobenzoyloxy succinimide (ANB-NOS), is used to form photo-adducts on the graphitic surfaces in a solid-state photochemical reaction, resulting in active ester groups being oriented for the subsequent reactions. In the second step, pre-synthesized DNA strands bearing a terminal amine group are coupled in an aqueous solution with the active esters on the photo-adducts. The versatility of the method is demonstrated by attaching pre-synthesized DNA to surfaces of carbon nanotubes in two platforms—as vertically-aligned multi-walled carbon nanotubes on a solid support and as tangled single-walled carbon nanotubes in mats. The reaction products at various stages were characterized by x-ray photoelectron spectroscopy. Two different assays were used to check that the DNA strands attached to the carbon nanotubes were able to bind their partner strands with complementary base sequences. The first assay, using partner DNA strands tethered to gold nanoparticles, enabled the sites of DNA attachment to the carbon nanotubes to be identified in TEM images. The second assay, using radioactively labelled partner DNA strands, quantified the density of functional DNA strands attached to the carbon nanotubes. The diversity of potential applications for these DNA-modified carbon-nanotube platforms is exemplified here by the successful use of a DNA-modified single-walled carbon-nanotube mat as an electrode for the specific detection of metal ions. (paper)

  8. 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...

  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. 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...

  11. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  12. 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

  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. 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.

  15. 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.

  16. 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.

  17. 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.

  18. In vivo click reaction between Tc-99m-labeled azadibenzocyclooctyne-MAMA and 2-nitroimidazole-azide for tumor hypoxia targeting.

    Science.gov (United States)

    Sun, Wenjing; Chu, Taiwei

    2015-10-15

    The bioactivity of nitroimidazole in Tc-99m-labeled 2-nitroimidazole, a traditional solid tumor hypoxia-imaging agent for single photon emission computed tomography (SPECT), is reduced by the presence of large ligand and metallic radionuclide, exhibiting lower tumor-to-nontumor ratios. In an effort to solve this general problem, a pretargeting strategy based on click chemistry (strain-promoted cyclooctyne-azide cycloaddition) was applied. The functional click synthons were synthesized as pretargeting components: an azide group linked to 2-nitroimidazole (2NIM-Az) serves for tumor hypoxia-targeting and azadibenzocyclooctyne conjugated with monoamine monoamide dithiol ligand (AM) functions as radiolabeling and binding group to azides in vivo. 2NIM-triazole-MAMA was obtained from in vitro click reaction with a reaction rate constant of 0.98M(-1)s(-1). AM and 2NIM-triazole-MAMA were radiolabeled with Tc-99m. The hypoxia-pretargeting biodistribution was studied in Kunming mice bearing S180 tumor; (99m)Tc-AM and (99m)Tc-triazole-2NIM were used as blank control and conventional control. Compared to the control groups, the pretargeting experiment exhibits the best radio-uptake and retention in tumor, with higher tumor-to-muscle and tumor-to-blood ratios (up to 8.55 and 1.44 at 8h post-(99m)Tc-complex-injection, respectively). To some extent, the pretargeting strategy protects the bioactivity of nitroimidazole and therefore provides an innovative approach for the development of tumor hypoxia-SPECT imaging agents. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Site-specific bioconjugation of a murine dihydrofolate reductase enzyme by copper(I-catalyzed azide-alkyne cycloaddition with retained activity.

    Directory of Open Access Journals (Sweden)

    Sung In Lim

    Full Text Available Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC is an efficient reaction linking an azido and an alkynyl group in the presence of copper catalyst. Incorporation of a non-natural amino acid (NAA containing either an azido or an alkynyl group into a protein allows site-specific bioconjugation in mild conditions via CuAAC. Despite its great potential, bioconjugation of an enzyme has been hampered by several issues including low yield, poor solubility of a ligand, and protein structural/functional perturbation by CuAAC components. In the present study, we incorporated an alkyne-bearing NAA into an enzyme, murine dihydrofolate reductase (mDHFR, in high cell density cultivation of Escherichia coli, and performed CuAAC conjugation with fluorescent azide dyes to evaluate enzyme compatibility of various CuAAC conditions comprising combination of commercially available Cu(I-chelating ligands and reductants. The condensed culture improves the protein yield 19-fold based on the same amount of non-natural amino acid, and the enzyme incubation under the optimized reaction condition did not lead to any activity loss but allowed a fast and high-yield bioconjugation. Using the established conditions, a biotin-azide spacer was efficiently conjugated to mDHFR with retained activity leading to the site-specific immobilization of the biotin-conjugated mDHFR on a streptavidin-coated plate. These results demonstrate that the combination of reactive non-natural amino acid incorporation and the optimized CuAAC can be used to bioconjugate enzymes with retained enzymatic activity.

  20. Novel Synthesis of 1,2,3-Triazoles via 1,3-Dipolar Cycloadditions of Alkynes to Azides in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    ZHONG,Ping(钟平); GUO,Sheng-Rong(郭圣荣)

    2004-01-01

    2-Azido-3,5-dichloropyridine and 2-azido-5-chloro-3-fluoropyridine were given by reaction of sodium azide with 2,3,5-trichloropyridine, 3,5-dichloro-2-fluoropyridine or 5-chloro-2,3-difiuoropyridine in ionic liquids.1,3-Dipolar cycloaddition of 2-azido-3,5-dichloropyridine or 2-azido-5-chloro-3-fluoropyridine to alkynes in ionic liquids afforded the corresponding 1,4,5-trisubstituted [1,2,3]-triazoles in good yields and regioselectivities.

  1. Ultrasound-promoted organocatalytic enamine–azide [3 + 2] cycloaddition reactions for the synthesis of ((arylselanylphenyl-1H-1,2,3-triazol-4-ylketones

    Directory of Open Access Journals (Sweden)

    Gabriel P. Costa

    2017-04-01

    Full Text Available The use of sonochemistry is described in the organocatalytic enamine–azide [3 + 2] cycloaddition between 1,3-diketones and aryl azidophenyl selenides. These sonochemically promoted reactions were found to be amenable to a range of 1,3-diketones or aryl azidophenyl selenides, providing an efficient access to new ((arylselanylphenyl-1H-1,2,3-triazol-4-ylketones in good to excellent yields and short reaction times. In addition, this protocol was extended to β-keto esters, β-keto amides and α-cyano ketones. Selanyltriazoyl carboxylates, carboxamides and carbonitriles were synthesized in high yields at short times of reaction under very mild reaction conditions.

  2. The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: Implications for the enzyme mechanism‡

    OpenAIRE

    Ogura, Hiroshi; Evans, John P.; Peng, Dungeng; Satterlee, James D.; de Montellano, Paul R. Ortiz; Mar, Gerd N. La

    2009-01-01

    The active site electronic structure of the azide complex of substrate-bound human heme oxygenase-1, (hHO) has been investigated by 1H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. 2D 1H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts, that places the lone iron π-spin in the dxz orbital, rather than the dyz orbital found in the cya...

  3. Simultaneous determination of inorganic and organic anions by ion chromatography

    International Nuclear Information System (INIS)

    Park, Yang Soon; Joe, Ki Soo; Han, Sun Ho; Park, Soon Dal; Choi, Kwang Soon

    1999-06-01

    Four methods were investigated for the simultaneous determination of several inorganic and organic anions in aqueous solution by ion chromatography. The first is two columns coupled system. The second is the gradient elution system with an anion exchange column. The third is the system with a mixed-mode stationary phase. The fourth is the system with an anion exchange column and the eluant of low conductivity without ion suppressor. The advantages and disadvantages of individual systems were discussed. The suitable methods were proposed for the application to the samples of the nuclear power industry and the environment. (author)

  4. 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.

  5. 2D and 3D surface photopatterning via laser-promoted homopolymerization of a perfluorophenyl azide-substituted BODIPY.

    Science.gov (United States)

    Raffy, Guillaume; Bofinger, Robin; Tron, Arnaud; Guerzo, André Del; McClenaghan, Nathan D; Vincent, Jean-Marc

    2017-11-09

    An innovative photopatterning process is described that allows, in a single laser-promoted operation, the covalent attachment of a molecule on a surface (2D patterning - xy dimensions) and its photopolymerization to grow micro-/nanostructures with spatial control in a third z-dimension. The surface patterning process, based on nitrene reactivity, was harnessed using the highly fluorescent azide-substituted boron difluoride dipyrromethene (BODIPY) 1 that was prepared in a single synthetic step from the parent pentafluorophenyl BODIPY on reacting with NaN 3 . Using the laser of a fluorescence microscope (375 nm or 532 nm) 1 could be grafted on adapted surfaces and then homopolymerised. In this study we show that using glass coverslips coated with PEG/high density alkyne groups (density of ∼1 × 10 14 per cm 2 ), the patterning process was much more spatially confined than when using PEG only coating. Varying the irradiation time (1 to 15 s) or laser power (0.14-3.53 μW) allowed variation of the amount of deposited BODIPY to afford, in the extreme case, pillars of a height up to 800 nm. AFM and MS studies revealed that the nano/microstructures were formed of particles of photopolymerized 1 having a mean diameter of ca. 30 nm. The emission spectra and fluorescence lifetimes for the patterned structures were measured, revealing a red-shift (from ∼560 nm up to 620 nm) of the maximum emission and a shortening (from ∼6 ns to 0.8 ns) of the fluorescence lifetimes in areas where the density of BODIPY is high. As an application of the patterning process, a figure formed of 136 dots/pillars was prepared. The confocal hyperspectral fluorescence image revealed that the figure is clearly resolved and constituted by highly photoluminescent red dots whose fluorescence intensities and emission color proved to be highly reproducible. SEM and AFM studies showed that the luminescent dots were pillars with a conical shape, an average height of 710 ± 28 nm and a FWHM of 400 ± 20

  6. A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives

    Directory of Open Access Journals (Sweden)

    Hicham Ben El Ayouchia

    2016-10-01

    Full Text Available The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.

  7. The concern of emergence of multi-station reaction pathways that might make stepwise the mechanism of the 1,3-dipolar cycloadditions of azides and alkynes

    Science.gov (United States)

    Mohtat, Bita; Siadati, Seyyed Amir; Khalilzadeh, Mohammad Ali; Zareyee, Daryoush

    2018-03-01

    After hot debates on the concerted or stepwise nature of the mechanism of the catalyst-free 1,3-dipolar cycloadditions (DC)s, nowadays, it is being believed that for the reaction of each dipole and dipolarophile, there is a possibility that the reaction mechanism becomes stepwise, intermediates emerge, and the reaction becomes non-stereospecific. Yield of even minimal amounts of unwanted side products or stereoisomers as impurities could bring many troubles like difficult purification steps. In this project, we have made attempts to study all probable reaction channels of the azide cycloadditions with two functionalized alkynes, in order to answer this question: "is there any possibility that intermediates evolve in the catalyst-free click 1,3-DC reaction of azide-alkynes?". During the calculations, several multi-station reaction pathways supporting the stepwise and concerted mechanisms were detected. Also, the born-oppenheimer molecular dynamic (BOMD) simulation was used to find trustable geometries which could be emerged during the reaction coordinate.

  8. Electron-transporting layer doped with cesium azide for high-performance phosphorescent and tandem white organic light-emitting devices

    Science.gov (United States)

    Yu, Yaoyao; Chen, Xingming; Jin, Yu; Wu, Zhijun; Yu, Ye; Lin, Wenyan; Yang, Huishan

    2017-07-01

    Cesium azide was employed as an effective n-dopant in the electron-transporting layer (ETL) of organic light-emitting devices (OLEDs) owing to its low deposition temperature and high ambient stability. By doping cesium azide onto 4,7-diphenyl-1,10-phenanthroline, a green phosphorescent OLED having best efficiencies of 66.25 cd A-1, 81.22 lm W-1 and 18.82% was realized. Moreover, the efficiency roll-off from 1000 cd m-2 to 10 000 cd m-2 is only 12.9%, which is comparable with or even lower than that of devices utilizing the co-host system. Physical mechanisms for the improvement of device performance were studied in depth by analyzing the current density-voltage (J-V) characteristics of the electron-only devices. In particular, by comparing the J-V characteristics of the electron-only devices instead of applying the complicated ultraviolet photoelectron spectrometer measurements, we deduced the decrease in barrier height for electron injection at the ETL/cathode contact. Finally, an efficient tandem white OLED utilizing the n-doped layer in the charge generation unit (CGU) was constructed. As far as we know, this is the first report on the application of this CGU for fabricating tandem white OLEDs. The emissions of the tandem device are all in the warm white region from 1213 cd m-2 to 10870 cd m-2, as is beneficial to the lighting application.

  9. Nitrate Anion Exchange in Pu-238 Aqueous Scrap Recovery Operations

    International Nuclear Information System (INIS)

    Pansoy-Hjelvik, M.E.; Silver, G.L.; Reimus, M.A.H.; Ramsey, K.B.

    1999-01-01

    Strong base, nitrate anion exchange (IX) is crucial to the purification of 238 Pu solution feedstocks with gross levels of impurities. This paper discusses the work involved in bench scale experiments to optimize the nitrate anion exchange process. In particular, results are presented of experiments conducted to (a) demonstrate that high levels of impurities can be separated from 238 Pu solutions via nitrate anion exchange and, (b) work out chemical pretreatment methodology to adjust and maintain 238 Pu in the IV oxidation state to optimize the Pu(IV)-hexanitrato anionic complex sorption to Reillex-HPQ resin. Additional experiments performed to determine the best chemical treatment methodology to enhance recovery of sorbed Pu from the resin, and VIS-NIR absorption studies to determine the steady state equilibrium of Pu(IV), Pu(III), and Pu(VI) in nitric acid are discussed

  10. 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

  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. 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. 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.

  14. Two independent anion transport systems in rabbit mandibular salivary glands

    DEFF Research Database (Denmark)

    Novak, I; Young, J A

    1986-01-01

    Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion in the foll......Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion...... stimulated secretion by about 30%, but when infused in addition to furosemide (0.1 mmol/l), it inhibited by about 20%. Amiloride (1.0 mmol/l) caused no inhibition. The results suggest that there are at least three distinct carriers in the rabbit mandibular gland. One is a furosemide-sensitive Na-coupled Cl...

  15. Mechanism of protection of adenosine from sulphate radical anion ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

  16. 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

  17. Intestinal transporters for endogenic and pharmaceutical organic anions

    DEFF Research Database (Denmark)

    Grandvuinet, Anne Sophie; Vestergaard, Henrik Tang; Rapin, Nicolas

    2012-01-01

    This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations....

  18. 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.

  19. Adsorption and desorption dynamics of citric acid anions in soil

    KAUST Repository

    Oburger, E.; Leitner, D.; Jones, D. L.; Zygalakis, K. C.; Schnepf, A.; Roose, T.

    2011-01-01

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal

  20. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flá vio; Rodrigues, Joã o M M; Farinha, Andreia; Cavaleiro, José A S; Tomé , Joã o P C

    2016-01-01

    promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  1. Changing certain dietary cationic and anionic minerals: Impact on ...

    African Journals Online (AJOL)

    Changing certain dietary cationic and anionic minerals: Impact on blood chemistry, milk ... Increased blood pH and serum HCO3 were noticed in buffaloes fed with LC ... Serum calcium and chloride increased with decreased DCAD level while ...

  2. 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.

  3. (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.)

  4. Determination of nitrate by anion exchange with ultraviolet detection

    Energy Technology Data Exchange (ETDEWEB)

    McComas, J.G.

    1976-01-01

    A weak base anion exchange resin is synthesized by surface bonding 3-aminopropyltriethoxysilane to silica gel. This silylated silica gel is used to separate nitrate from interferences. The nitrate is then determined by measuring its absorbance at 220 nm. An interference study was performed and no anions commonly found in potable water interferes. A comparison of this method was made with the brucine method on real samples and satisfactory agreement was obtained between the two methods.

  5. 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

  6. 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.

  7. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Science.gov (United States)

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  8. 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.

  9. 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.

  10. Poli (metil azoteto de glicidila - GAP. I: síntese e caracterização Glycidyl azide polymer (GAP. I: syntheses and characterization

    Directory of Open Access Journals (Sweden)

    Sandro P. Ribeiro

    2012-01-01

    Full Text Available O poli (metil azoteto de glicidila - GAP - é um material energético que pode ser utilizado como aglutinante (binder e como plastificante energético em compostos explosivos e propulsores de foguetes. Neste trabalho, foi abordada a síntese do (GAP através da conversão direta da epicloridrina (ECH a GAP. Os reagentes utilizados foram azida de sódio, epicloridrina e vários álcoois extensores de cadeias, o etanodiol, o 1,4-butanodiol, o dietilenoglicol e o glicerol. Alguns parâmetros de operação foram avaliados, como o tempo de reação, a proporção entre os reagentes, dois tipos de solvente e a ordem de adição dos reagentes. A variável observada para a análise foi a massa molecular do GAP. Todos os materiais sintetizados também foram caracterizados por análises de FTIR, UV, RMN, DSC, análise elementar e TGA. Uma maior massa molecular, maior rendimento e uma melhor conversão do grupo azida a GAP foram obtidos com a adição de epicloridrina sobre a azida de sódio e usando DMF como solvente.GAP is an aliphatic polyether that includes hydroxyl groups and highly energetic azide groups. Thus, it is an energetic material that can be used as binder or plasticizing agent in propellants and explosive mixtures. The glycidyl azide polymer (GAP was synthesized and characterized by direct conversion of epichlorohydrin. GAP was synthesized by reaction of sodium azide, epichlorohydrin, and some extensor alcohols. The investigation focused on the effects of some key reaction parameters including reagent proportions, reaction time and two different solvents. The product was characterized by FTIR, UV, NMR, DSC, elemental analysis, TGA and GPC. The species were also evaluated through molecular weight (GPC, glass transition temperature (DSC, ignition time and sensitivity.

  11. Rational design of azide-bridged bimetallic complexes. Crystal structure and magnetic properties of Fe(III)MFe(III) (M = Ni(II) and Cu(II)) trinuclear species.

    Science.gov (United States)

    Colacio, Enrique; Costes, Jean-Pierre; Domínguez-Vera, José M; Maimoun, Ikram Ben; Suárez-Varela, José

    2005-01-28

    The first examples of azide-bridged bimetallic trinuclear complexes ([M(cyclam)][FeL(N3)(mu1,5-N3)]2) (H2L = 4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene) have been structurally and magnetically characterized.

  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. 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)

  14. 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)

  15. 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)].

  16. 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.

  17. 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.

  18. 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.

  19. Solvent-resistant small molecule solar cells by roll-to-roll fabrication via introduction of azide cross-linkable group

    DEFF Research Database (Denmark)

    Chen, Mei-Rong; Fan, Cong-Cheng; Andersen, Thomas Rieks

    2014-01-01

    A novel cross-linkable azide-functionalized diketopyrrolopyrrole based compound DPP(BT-N-3)(2) was designed and synthesized via Stille coupling. Cross-linking of such molecule could help us fabricate insoluble film which could be used to fabricate heterostructures through solution processing......, without dissolving the pre-patterned layers. In order to investigate the photovoltaic performances of the newly synthesized compound, large area solar cells were produced by roll coating technique. Two set of devices were fabricated by employing DPP(BT-N-3)(2) as either an electron donor or acceptor....... A best power conversion efficiency of 0.067%, combined with an open circuit voltage of 0.53 V, and a fill factor of 37.6% were obtained for the device with DPP(BT-N-3)(2) as an electron acceptor. In addition, we could prove that the large area small molecule based organic solar cells could be fabricated...

  20. The effects of duration of pre-soaking treatments on the frequency and spectrum of mutations induced by sodium azide in CES 14 Mungbean variety

    International Nuclear Information System (INIS)

    Asencion, A.B.

    1982-04-01

    Seeds of mungbean variety CES 14 were treated with 10 - 3 sodium azide for 2 hours buffered at pH 3 after various pre-soaking treatment durations of 0, 4, 6, 8, 10, 12, 14 and 16 hours. The biological parameters that were significantly affected by the treatments in the M 1 were germination, seedling height and survival. The chlorophyll and other morphological mutations in the M 2 gradually increased with increasing pre-soaking time. The treatment that had the lowest mutation rate was the 16-hour pre-soaked seeds. No chlorophyll mutation was noted in both the water and buffer control. One variant was noted, however, in the buffer control. (author)

  1. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    International Nuclear Information System (INIS)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

    2009-01-01

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  2. Effects of UVA irradiation, aryl azides, and reactive oxygen species on the orthogonal inactivation of the human immunodeficiency virus (HIV-1)

    International Nuclear Information System (INIS)

    Belanger, Julie M.; Raviv, Yossef; Viard, Mathias; Cruz, M. Jason de la; Nagashima, Kunio; Blumenthal, Robert

    2011-01-01

    Previously we reported that hydrophobic aryl azides partition into hydrophobic regions of the viral membrane of enveloped viruses and inactivate the virus upon UVA irradiation for 2 min. Prolonged irradiation (15 min) resulted in viral protein aggregation as visualized via Western blot analysis, due to reactive oxygen species (ROS) formation, with preservation of the surface antigenic epitopes. Herein, we demonstrate that these aggregates show detergent resistance and that this property may be useful towards the creation of a novel orthogonal virus inactivation strategy for use in preparing experimental vaccines. When ROS-modified HIV virus preparations were treated with 1% Triton X-100, there was an increase in the percent of viral proteins (gp41, p24) in the viral pellet after ultracentrifugation through sucrose. Transmission electron microscopy (TEM) of these detergent-resistant pellets shows some recognizable virus fragments, and immunoprecipitation studies of the gp41 aggregates suggest the aggregation is covalent in nature, involving short-range interactions.

  3. Evaluation Of GAMMA And Sodium Azide Radiation Looking For Resistance To MACROPHOMINA Phaseoli T. In Three Promissory Lines Of Benne Sesamum Indicum L

    International Nuclear Information System (INIS)

    Lopez R, Liliana V.; Melo O, Mario E.; Reina C, Yasmin

    1993-01-01

    The Benne in Colombia is a cultivation relegated to small properties and its main problem is the withering (Macrophomina phaseoli T.) which may cause losses of the cent per cent. Situation that generated the interest to carry out a study on induction of mutations in this species, using Gamma Rays and Sodium Azide with the purpose of obtaining possible resistant mutants to the mushroom. The initial stage of the work, determination of good dose, was developed in the INEA in Bogota and the field evaluation in the ICA Nataima in Espinal. A rehearsal was mounted to evaluate germination and plants height in the lines Cycle 0 - PlO, ENA 841-3 and ENA 841-5 tried with the doses (OR, 25, 50, 75 and 100) krad of gamma rays and (OR, 5, 10, 15 and 20) mm of Sodium Azide, the obtained information was processed using a Complete Blocks design at random with Factorial arrangement 3x5 and test of Duncan, based on the obtained data the Curves of Radio and chemical sensitivity were determined. Then the massive treatment of the seed was made with the optimum mutagenic dose and it was taken to field (Ml), giving it good conditions for the development of the cultivation. The test of chlorophyll ian mutants was applied to the seed harvested M2 to select the treatment with which the program of improvement should continue, it was sowed in a lot with high pressure of selection of the mushroom and an inter and intra family selection was made

  4. Comparison Of The Caused Physiologic Effects For The GAMMA Radiations And The Sodium Azide (NAN3) In Four Genotypes Of Wheat

    International Nuclear Information System (INIS)

    Quevedo C, Luis A.

    1994-01-01

    As it happens in many countries of the world. The wheat occupies an important line in the feeding of the Colombian town, what demands the continuous obtaining of new cultivations to assist the necessities of the farmers and consumers. The induction of mutations is a tool by means of which excellent results have been obtained in the improvement of cereals, especially in wheat, rice and barley, where mutants have been obtained that have been used directly by the farming ones and indirectly for the programs of improvement. Keeping in mind that in Colombia it is sought to use the induction of mutations in the programs of wheat improvement, and that it doesn't have deep investigations in this respect, it was solved to carry out the present work, where the main objective was to compare the tired physiologic effects after the treatment with different dose and concentrations of gamma rays and sodium azide in four genotypes of wheat of national interest. The work was carried out in two phases, the first one (generation M1) in the one that the seeds of the four genotypes were sowed (ICA-Tenza, Pav -76, Bonza-63 and Creole Pelao) tried with dose of 0, 10, 20, 30 and 40 krad of gamma rays and concentrations of 0, 0.1, 0.2, 0.3 and 0.4 m Molar of sodium azide. The data have more than enough emergency, plant height, longitude of the spike, grains/tassel number and weight of 100 grains, they were tabulated, processed and drawing for each one of the treatments being obtained this way, the radio curves and chemical- sensitivity. The second phase denominated generation M2, makes reference to the seeds coming from the plants M1, which were collected in form singular, taking 2 tassel/plant of the total of plants survivors planted in field

  5. Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

    2017-06-01

    Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  6. Electron-transporting layer doped with cesium azide for high-performance phosphorescent and tandem white organic light-emitting devices

    International Nuclear Information System (INIS)

    Yu, Yaoyao; Chen, Xingming; Jin, Yu; Wu, Zhijun; Yu, Ye; Lin, Wenyan; Yang, Huishan

    2017-01-01

    Cesium azide was employed as an effective n-dopant in the electron-transporting layer (ETL) of organic light-emitting devices (OLEDs) owing to its low deposition temperature and high ambient stability. By doping cesium azide onto 4,7-diphenyl-1,10-phenanthroline, a green phosphorescent OLED having best efficiencies of 66.25 cd A −1 , 81.22 lm W −1 and 18.82% was realized. Moreover, the efficiency roll-off from 1000 cd m −2 to 10 000 cd m −2 is only 12.9%, which is comparable with or even lower than that of devices utilizing the co-host system. Physical mechanisms for the improvement of device performance were studied in depth by analyzing the current density–voltage ( J – V ) characteristics of the electron-only devices. In particular, by comparing the J – V characteristics of the electron-only devices instead of applying the complicated ultraviolet photoelectron spectrometer measurements, we deduced the decrease in barrier height for electron injection at the ETL/cathode contact. Finally, an efficient tandem white OLED utilizing the n-doped layer in the charge generation unit (CGU) was constructed. As far as we know, this is the first report on the application of this CGU for fabricating tandem white OLEDs. The emissions of the tandem device are all in the warm white region from 1213 cd m −2 to 10870 cd m −2 , as is beneficial to the lighting application. (paper)

  7. An Anthracene-Based Tripodal Chemosensor for Anion Sensing

    Directory of Open Access Journals (Sweden)

    Whitney A. Quinn

    2010-05-01

    Full Text Available An anthracene-based tripodal ligand was synthesized from the condensation of tren with 9-anthraldehyde, and the subsequent reduction with sodium borohydride. The neutral ligand was protonated from the reaction with p-toluenesulfonic acid to give a triply charged chemosensor that was examined for its anion binding ability toward fluoride, chloride, bromide, sulfate and nitrate by the fluorescence spectroscopy in DMSO. The addition of an anion to the ligand resulted in an enhancement in fluorescence intensity at the excitation of 310 nm. Analysis of the spectral changes suggested that the ligand formed a 1:1 complex with each of the anions, showing strong affinity for fluoride and sulfate in DMSO. The unsubstituted tren was reacted with sulfuric acid to form a sulfate complex and the structure was determined by the X-ray crystallography. Analysis of the complex revealed that three sulfates are held between two ligands by multiple hydrogen bonding interactions with protonated amines.

  8. 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

  9. 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.

  10. Reactivity of niobium cluster anions with nitrogen and carbon monoxide

    Science.gov (United States)

    Mwakapumba, Joseph; Ervin, Kent M.

    1997-02-01

    Reactions of small niobium cluster anions, Nbn-(n = 2-7), with CO and N2 are investigated using a flow tube reactor (flowing afterglow) apparatus. Carbon monoxide chemisorption on niobium cluster anions occurs with faster reaction rates than nitrogen chemisorption on corresponding cluster sizes. N2 addition to niobium cluster anions is much more size-selective than is CO addition. These general trends follow those reported in the literature for reactions of neutral and cationic niobium clusters with CO and N2. Extensive fragmentation of the clusters is observed upon chemisorption. A small fraction of the larger clusters survive and sequentially add multiple CO or N2 units without fragmentation. However, chemisorption saturation is not reached at the experimentally accessible pressure and reagent concentration ranges. The thermochemistry of the adsorption processes and the nature of the adsorbed species, molecular or dissociated, are discussed.

  11. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  12. 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.

  13. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    International Nuclear Information System (INIS)

    Ye Jiesheng; Liu Chunxi; Chen Zhijin; Zhang Na; Wang Aihua

    2008-01-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (≤20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo

  14. Synthesis of meta-substituted monodentate phosphinite ligands and ...

    Indian Academy of Sciences (India)

    SATEJ S DESHMUKH

    from organic synthesis, phosphinite ligands find appli- cations in a variety of ... thesis of meta-substituted phosphinite ligands is rarely reported.18 This is most ... 1.9 μm; mobile phase used, 90% methanol + 10% water +. 0.1% formic acid) ...

  15. 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)

  16. 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

  17. A study of model systems in anionic exchange

    International Nuclear Information System (INIS)

    Haegele, R.; Boeyens, J.C.A.

    1977-01-01

    Preliminary experiments are reported on the preparation and characterization of anionic sulphate and chloride complexes of UO 2+ 2 and iron(III), benzyl-trimethylammonium cation being used as a model substance for the simulation of positive sites in an anionic-exchange resin. The structure of (BTMA) 4 [UO 2 CL 3 -O 2 -CL 3 UO 2 ], a binuclear uranyl-peroxocomplex that has not been reported in the literature, was elucidated by single-crystal x-ray examination, and is described and discussed [af

  18. Procedure for reducing hydrogen ion concentration in acidic anion eluate

    International Nuclear Information System (INIS)

    Parobek, P.; Baloun, S.; Plevac, S.

    1992-01-01

    A procedure is suggested for reducing the concentration of hydrogen ions in the acidic anionic eluate formed during the separation of uranium. The procedure involves anex elution, precipitation, filtration, precipitate rinsing, and anex rinsing. The procedure is included in the uranium elution process and requires at least one ion exchanger column and at least one tank in the continuous or discontinuous mode. Sparing the neutralizing agent by reducing the hydrogen ion concentration in the acidic anionic eluate is a major asset of this procedure. (Z.S.). 1 fig

  19. 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...

  20. 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.

  1. Uranium extraction from sulfuric acid solution using anion exchange resin

    International Nuclear Information System (INIS)

    Sheta, M. E.; Abdel Aal, M. M.; Kandil, A. T.

    2012-12-01

    Uranium is currently recovered from sulfuric acid leach liquor using anion exchange resin as Amberlite IRA 402 (CT). This technology is based on fact that, uranium exists as anionic complexes. This takes place by controlling the pH of the solution, agitation time, temperature and resin to solution ratio (R/S). In this work, batch stirrer tank used for uranium extraction from sulfate medium and after extraction, elution process was done using 1M NaCl solution. After extraction and elution process, the resin was separated from the system and uranium was determined in the solution. (Author)

  2. 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)

  3. 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.

  4. Equilibrium and Thermodynamic Studies of Anionic Dyes Removal by an Anionic Clay-Layered Double Hydroxide

    International Nuclear Information System (INIS)

    Kantasamy, N.; Siti Mariam Sumari

    2016-01-01

    Adsorption isotherm describes the interaction of adsorbates with adsorbent in equilibrium. Equilibrium data was examined using Langmuir and Freundlich isotherm models. Thermodynamic studies were used to evaluate the thermodynamic parameters; heat of enthalpy change (ΔH degree), Gibbs free energy change (ΔG degree) and heat of entropy change (ΔSdegree) in order to gain information regarding the nature of adsorption (exothermic or endothermic). Four reactive dyes of anionic type, Acid Blue 29 (AB29), Reactive Black 5 (RB5), Reactive Orange 16 (RO16) and Reactive Red 120 (RR120) were used to obtain equilibrium isotherms at 25, 35, 45 and 55 degree Celsius. Based on Giles' classification, the isotherm produced were of L2-type, indicating strong dye affinity towards the adsorbent, and with weak competition with the solvent molecules for active adsorption sites. Equilibrium data fitted both Langmuir and Freundlich isotherm models with high correlation coefficient (R"2 > 0.91) indicating the possibility of both homogeneity and heterogeneous nature of adsorption. The negative values of ΔGdegree indicate the adsorption processes were spontaneous and feasible. The negative values of ΔHdegree lie between -20 to -75 kJ/ mol, suggesting these processes were exothermic and physical in nature. The negative values of ΔSdegree are indication of decreased disorder and randomness of spontaneous adsorption of reactive dyes on layered double hydroxide as adsorbent. (author)

  5. 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).

  6. Anionic construction of the SLq,s(2) algebra

    International Nuclear Information System (INIS)

    Matheus-Valle, J.L.; Monteiro, M.R.

    1993-01-01

    Considering anionic oscillators in a two-dimensional lattice, the quantum semi-group sl (q,s ) (2) is realized by means of a generalized Schwinger construction. It is found that the parameter q of the algebra is connected to the statistical parameter, whereas the s parameter is related to a s-deformed oscillator introduced at each point of the lattice. (author)

  7. 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.

  8. Adsorption and intercalation of anionic surfactants onto layered ...

    Indian Academy of Sciences (India)

    Unknown

    Department of Polymer Technology, Kamaraj College of Engineering and Technology, Virudhunagar 626 ... Layered double hydroxides (LDH) with brucite like structure was modified with various anionic ... Recently the application of layered double hydroxides ..... Yuan Q, Wei M, Wang Z and Duan X 2004 Clays Clay Miner.

  9. Contribution of attendant anions on cadmium toxicity to soil enzymes.

    Science.gov (United States)

    Tian, Haixia; Kong, Long; Megharaj, Mallavarapu; He, Wenxiang

    2017-11-01

    Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO 4 2- , NO 3 - , Cl - , and Ac - ) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO 4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO 3 - displayed a similar behavior with Cl - on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. 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.

  11. 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.

  12. based anion exchange membrane for alkaline polymer electrolyte

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Hydroxyl ion (OH–) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl.

  13. Anion-exchange membranes in electrochemical energy systems

    NARCIS (Netherlands)

    Varcoe, J.R.; Atanassov, P.; Dekel, D.R.; Herring, A.M.; Hickner, M.A.; Kohl, P.A.; Kucernak, A. R.; Mustain, W.E.; Nijmeijer, K.; Scott, Keith; Xu, Tongwen; Zhuang, Lin

    2014-01-01

    This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current

  14. Anion complexation by calix[4]arene–TTF conjugates

    Czech Academy of Sciences Publication Activity Database

    Flídrová, K.; Tkadlecová, M.; Lang, Kamil; Lhoták, P.

    2012-01-01

    Roč. 92, č. 1 (2012), s. 668-673 ISSN 0143-7208 R&D Projects: GA ČR GA203/09/0691 Institutional research plan: CEZ:AV0Z40320502 Keywords : calix[4]arene * tetrathiafulvalene * anion recognition * receptor * NMR titration * UV/vis spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.532, year: 2012

  15. Novel Biscalix[4]arene-based Anion Receptors

    Czech Academy of Sciences Publication Activity Database

    Šťastný, V.; Lhoták, P.; Michlová, V.; Stibor, I.; Sýkora, Jan

    2002-01-01

    Roč. 58, č. 36 (2002), s. 7207-7211 ISSN 0040-4020 R&D Projects: GA ČR GA104/00/1722; GA ČR GA203/00/1011 Keywords : calixarenes * anion receptors * NMR titration Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.420, year: 2002

  16. 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.

  17. 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 ...

  18. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  19. Alkylation of enolate anions formation of enol ethers

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  20. Synthesis of Terpyridine-Terminated Polymers by Anionic Polymerization

    NARCIS (Netherlands)

    Guerrero-Sanchez, C.A.; Lohmeijer, B.G.G.; Meier, M.A.R.; Schubert, U.S.

    2005-01-01

    The synthesis of terpyridine-functionalized polystyrene was achieved by reacting 4‘-chloro-2,2‘:6‘,2‘ ‘-terpyridine (terminating agent) with "living" polymeric carbanions synthesized by anionic polymerization. The obtained polymers were characterized by gel permeation chromatography, nuclear

  1. Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries.

    Science.gov (United States)

    Grayfer, Ekaterina D; Pazhetnov, Egor M; Kozlova, Mariia N; Artemkina, Sofya B; Fedorov, Vladimir E

    2017-12-22

    Classical Li-ion battery technology is based on the insertion of lithium ions into cathode materials involving metal (cationic) redox reactions. However, this vision is now being reconsidered, as many new-generation electrode materials with enhanced reversible capacities operate through combined cationic and anionic (non-metal) reversible redox processes or even exclusively through anionic redox transformations. Anionic participation in the redox reactions is observed in materials with more pronounced covalency, which is less typical for oxides, but quite common for phosphides or chalcogenides. In this Concept, we would like to draw the reader's attention to this new idea, especially, as it applies to transition-metal polychalcogenides, such as FeS 2 , VS 4 , TiS 3 , NbS 3 , TiS 4 , MoS 3 , etc., in which the key role is played by the (S-S) 2- /2 S 2- redox reaction. The exploration and better understanding of the anion-driven chemistry is important for designing advanced materials for battery and other energy-related applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The Determination of Anionic Surfactants in Natural and Waste Waters.

    Science.gov (United States)

    Crisp, P. T.; And Others

    1983-01-01

    Background information, procedures, and results of an experiment suitable for measuring subpart per million concentrations of anionic surfactants in natural waters and waste effluents are provided. The experiment required only a spectrophotometer or filter photometer and has been successfully performed by students in an undergraduate environmental…

  3. 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

  4. Adsorption and intercalation of anionic surfactants onto layered ...

    Indian Academy of Sciences (India)

    Layered double hydroxides (LDH) with brucite like structure was modified with various anionic surfactants containing sulfonate, carboxyl, phosphonate and sulfate end group through ion-exchange method. XRD reports indicated that the sulfonate group containing surfactants led to an adsorption process whereas the sulfate ...

  5. Evaluation of indigenous anion exchange resins for plutonium purification

    International Nuclear Information System (INIS)

    Kumaresan, R.; Sabharwal, K.N.; Srinivasan, T.G.; Vasudeva Rao, P.R.; Thite, B.S.; Ajithlal, R.T.; Sinalkar, Nitin; Dharampurikar, G.R.; Janardhanan, C.; Michael, K.M.; Vijayan, K.; Jambunathan, U.; Dey, P.K.

    2004-01-01

    Preliminary data with pure plutonium nitrate solution indicate that indigenous anion exchange resin can be used for the purification and concentration of plutonium. However, further studies are required to be conducted on larger scale with actual plant feed solutions before arriving to final conclusions. This includes repeated loading and elution cycles studies with the same bed and evaluation of the performance after each cycle

  6. Materials chemistry approach to anion-sensor design

    Czech Academy of Sciences Publication Activity Database

    Anzenbacher Jr., P.; Jursiková, K.; Aldakov, D.; Marquez, M.; Pohl, Radek

    2004-01-01

    Roč. 60, č. 49 (2004), s. 11163-11168 ISSN 0040-4020 Institutional research plan: CEZ:AV0Z4055905 Keywords : conductive polymer * anion sensing * polythiophene Subject RIV: CC - Organic Chemistry Impact factor: 2.643, year: 2004

  7. 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...

  8. Preparation of Acrylamide-based Anionic Polyelectrolytes for Soil Establishment

    Directory of Open Access Journals (Sweden)

    Ahmad Rabiee

    2012-12-01

    Full Text Available Synthetic water soluble acrylamide-based polymers have wide range of ap-plications  in  the  feld  of  soil  establishment  and  non-desertifcation.  In  this research, the acrylamide-based anionic polyelectrolytes were prepared by  solution polymerization. The polymerization was carried out using AIBN as a radical initiator and at different degrees of anionic charges ranging between 10% and 30% using sodium hydroxide as hydrolyzing agents. The chemical structure of the  synthetic polymers was studied and confrmed by FTIR technique. The charge density on polymer backbone was determined by titration method. The rheological behavior of polymer solutions was evaluated by Brookfeld viscometer. The results show that the viscosity decreases with increasing the shear rate of solutions. Molecular weights of samples were measured by laser light scattering analyzer. The morphology of the polymer was studied by SEM and the EDX was used for elemental analysis determination. The anionic polymers with 10-30% negative charges were mixed with clay in order to evaluate the soil establishment. The results show that an anionic polyelectro-lyte can make soil particles more cohesive and improve soil physical properties.

  9. Spectral modulation through controlling anions in nanocaged phosphors

    NARCIS (Netherlands)

    Bian, H.; Liu, Y.; Yan, D.; Zhu, H.; Liu, C.; Xu, C.S.; Liu, Y.; Zhang, H.; Wang, X.

    2013-01-01

    A new approach has been proposed and validated to modulate the emission spectra of europium-doped 12CaO center dot 7Al(2)O(3) phosphors by tuning the nonradiative and radiative transition rates, realized by controlling the sort and amount of the encaged anions. A single wavelength at 255 nm can

  10. The anionic biosurfactant rhamnolipid does not denature industrial enzymes

    Directory of Open Access Journals (Sweden)

    Jens Kvist Madsen

    2015-04-01

    Full Text Available Biosurfactants (BS are surface-active molecules produced by microorganisms. Their combination of useful properties and sustainable production make them promising industrial alternatives to petrochemical and oleochemical surfactants. Here we compare the impact of the anionic BS rhamnolipid (RL and the conventional/synthetic anionic surfactant sodium dodecyl sulfate (SDS on the structure and stability of three different commercially used enzymes, namely the cellulase Carezyme® (CZ, the phospholipase Lecitase Ultra® (LT and the α-amylase Stainzyme® (SZ. Our data reveal a fundamental difference in their mode of interaction. SDS shows great diversity of interaction towards the different enzymes. It efficiently unfolds both LT and CZ, but LT is unfolded by SDS through formation of SDS clusters on the protein well below the cmc, while CZ is only unfolded by bulk micelles and on average binds significantly less SDS than LT. SDS binds with even lower stoichiometry to SZ and leads to an increase in thermal stability. In contrast, RL does not affect the tertiary or secondary structure of any enzyme at room temperature, has little impact on thermal stability and only binds detectably (but at low stoichiometries to SZ. Furthermore all enzymes maintain activity at both monomeric and micellar concentrations of RL. We conclude that RL, despite its anionic charge, is a surfactant that does not compromise the structural integrity of industrially relevant proteins. This makes RL a promising alternative to current synthetic anionic surfactants in a wide range of commercial applications.

  11. 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

  12. Separation of anionic oligosaccharides by high-performance liquid chromatography

    International Nuclear Information System (INIS)

    Green, E.D.; Baenziger, J.U.

    1986-01-01

    The authors have developed methods for rapid fractionation of anionic oligosaccharides containing sulfate and/or sialic acid moieties by high-performance liquid chromatography (HPLC). Ion-exchange HPLC on amine-bearing columns (Micropak AX-10 and AX-5) at pH 4.0 is utilized to separate anionic oligosaccharides bearing zero, one, two, three, or four charges, independent of the identity of the anionic moieties (sulfate and/or sialic acid). Ion-exchange HPLC at pH 1.7 allows separation of neutral, mono-, di-, and tetrasialylated, monosulfated, and disulfated oligosaccharides. Oligosaccharides containing three sialic acid residues and those bearing one each of sulfate and sialic acid, however, coelute at pH 1.7. Since the latter two oligosaccharide species separate at pH 4.0, analysis at pH 4.0 followed by analysis at pH 1.7 can be utilized to completely fractionate complex mixtures of sulfated and sialylated oligosaccharides. Ion-suppression amine adsorption HPLC has previously been shown to separate anionic oligosaccharides on the basis of net carbohydrate content (size). In this study they demonstrate the utility of ion-suppression amine adsorption HPLC for resolving sialylated oligosaccharide isomers which differ only in the linkages of sialic acid residues (α2,3 vs α2,6) and/or location of α2,3- and α2,6-linked sialic acid moieties on the peripheral branches of oligosaccharides. These two methods can be used in tandem to separate oligosaccharides, both analytically and preparatively, based on their number, types, and linkages of anionic moieties

  13. 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.

  14. Polyvinyl alcohol (PVA) and sulfonated polyetheretherketone (SPEEK) anion exchange membrane for fuel cell

    CSIR Research Space (South Africa)

    Luo, H

    2010-08-31

    Full Text Available less than proton exchange membrane systems using alcohol as fuel. Many anion exchange membranes based on quaternised polymers have been developed and studied for AMFC3-5. The quaternary ammonium functional groups are the anion conductors...

  15. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers

    KAUST Repository

    Zhang, H.; Alkayal, N.; Gnanou, Yves; Hadjichristidis, Nikolaos

    2013-01-01

    A novel one-pot methodology combining anionic polymerization and polyhomologation, through a "bridge" molecule (BF3OEt 2), was developed for the synthesis of polyethylene (PE)-based block copolymers. The anionically synthesized macroanion reacts

  16. One-pot synthesis of novel 1-(1H-tetrazol-5-yl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine derivatives via an Ugi-azide 4CR process.

    Science.gov (United States)

    Ghandi, Mehdi; Salahi, Saleh; Taheri, Abuzar; Abbasi, Alireza

    2018-05-01

    A facile one-pot method has been developed for the synthesis of novel pyrrolo[2,1-a]pyrazine scaffolds. A variety of 1-(1H-tetrazol-5-yl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine derivatives were obtained in moderate to high yields in methanol using a one-pot four-component condensation of 1-(2-bromoethyl)-1H-pyrrole-2-carbaldehyde, amine, isocyanide and sodium azide at room temperature. These reactions presumably proceed via a domino imine formation, intramolecular annulation and Ugi-azide reaction. Unambiguous assignment of the molecular structures was carried out by single-crystal X-ray diffraction.

  17. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles

    Science.gov (United States)

    Sarwar, Atif; Katas, Haliza; Samsudin, Siti Noradila; Zin, Noraziah Mohamad

    2015-01-01

    Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP) and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC) of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene) triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide) triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68) demonstrated the safety; suggesting that these derivatives could be used in future

  18. Contribution of various metabolites to the "unmeasured" anions in critically ill patients with metabolic acidosis.

    NARCIS (Netherlands)

    Moviat, M.; Terpstra, A.M.; Ruitenbeek, W.; Kluijtmans, L.A.J.; Pickkers, P.; Hoeven, J.G. van der

    2008-01-01

    OBJECTIVE: The physicochemical approach, described by Stewart to investigate the acid-base balance, includes the strong ion gap (SIG), a quantitative measure of "unmeasured" anions, which strongly correlates to the corrected anion gap. The chemical nature of these anions is for the most part

  19. Using remote substituents to control solution structure and anion binding in lanthanide complexes

    DEFF Research Database (Denmark)

    Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.

    2013-01-01

    A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery ...

  20. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance. Final Report

    International Nuclear Information System (INIS)

    Bowman-James, Kristin

    2008-01-01

    increased understanding of the chemical rules that govern the selective sequestration of anions.

  1. Reactive Energetic Plasticizers Utilizing Cu-Free Azide-Alkyne 1,3-Dipolar Cycloaddition for In-Situ Preparation of Poly(THF-co-GAP-Based Polyurethane Energetic Binders

    Directory of Open Access Journals (Sweden)

    Mingyang Ma

    2018-05-01

    Full Text Available Reactive energetic plasticizers (REPs coupled with hydroxy-telechelic poly(glycidyl azide-co-tetrahydrofuran (PGT-based energetic polyurethane (PU binders for use in solid propellants and plastic-bonded explosives (PBXs were investigated. The generation of gem-dinitro REPs along with a terminal alkyne stemmed from a series of finely designed approaches to not only satisfy common demands as conventional energetic plasticizers, but also to prevent the migration of plasticizers. The miscibility and rheological behavior of a binary mixture of PGT/REP with various REP fractions were quantitatively determined by differential scanning calorimetry (DSC and rheometer, respectively, highlighting the promising performance of REPs in the formulation process. The kinetics on the distinct reactivity of propargyl vs. 3-butynyl species of REPs towards the azide group of the PGT prepolymer in terms of Cu-free azide-alkyne 1,3-dipolar cycloaddition (1,3-DPCA was studied by monitoring 1H nuclear magnetic resonance spectroscopy and analyzing the activation energies (Ea obtained using DSC. The thermal stability of the finally cured energetic binders with the incorporation of REPs indicated that the thermal stability of the REP/PGT-based PUs was maintained independently of the REP content. The tensile strength and modulus of the PUs increased with an increase in the REP content. In addition, the energetic performance and sensitivity of REP and REP triazole species was predicted.

  2. Tunable cytotoxicity of rhodamine 6G via anion variations.

    Science.gov (United States)

    Magut, Paul K S; Das, Susmita; Fernand, Vivian E; Losso, Jack; McDonough, Karen; Naylor, Brittni M; Aggarwal, Sita; Warner, Isiah M

    2013-10-23

    Chemotherapeutic agents with low toxicity to normal tissues are a major goal in cancer research. In this regard, the therapeutic activities of cationic dyes, such as rhodamine 6G, toward cancer cells have been studied for decades with observed toxicities toward normal and cancer cells. Herein, we report rhodamine 6G-based organic salts with varying counteranions that are stable under physiological conditions, display excellent fluorescence photostability, and more importantly have tunable chemotherapeutic properties. Our in vitro studies indicate that the hydrophobic compounds of this series allow production of nanoparticles which are nontoxic to normal cells and toxic to cancer cells. Furthermore, the anions, in combination with cations such as sodium, were observed to be nontoxic to both normal and cancer cells. To the best of our knowledge, this is the first demonstration that both the cation and anion play an extremely important and cooperative role in the antitumor properties of these compounds.

  3. Macrocyclic bis(ureas as ligands for anion complexation

    Directory of Open Access Journals (Sweden)

    Claudia Kretschmer

    2014-08-01

    Full Text Available Two macrocyclic bis(ureas 1 and 2, both based on diphenylurea, have been synthesized. Compound 1 represents the smaller ring with two ethynylene groups as linkers and 2 the larger ring with two butadiynylene groups. On thermal treatment to 130 °C molecule 1 splits up into two dihydroindoloquinolinone (3 molecules. Both compounds 1 and 2 form adducts with polar molecules such as dimethyl sulfoxide (DMSO and dimethylformamide (DMF and act as complexing agents towards a series of anions (Cl−, Br−, I−, NO3−, HSO4−. The crystal structures of 3, 2·2DMSO, 2·2DMF, and of the complex NEt4[Br·2] have been determined. Quantitative investigations of the complexation equilibria were performed via 1H NMR titrations. While 1 is a rather weak complexing agent, the large ring of 2 binds anions with association constants up to log K = 7.93 for chloride ions.

  4. 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.

  5. Thermal Properties of Anionic Polyurethane Composition for Leather Finishing

    Directory of Open Access Journals (Sweden)

    Olga KOVTUNENKO

    2016-09-01

    Full Text Available Thermal properties of anionic polyurethane composition mixed with collagen product and hydrophilic sodium form of montmorillonite for use in the finishing of leather were studied by thermogravimetric method. The thermal indices of processes of thermal and thermo-oxidative destruction depending on the polyurethane composition were determined. The influence of anionic polyurethane composition on thermal behavior of chromium tanned gelatin films that imitate the leather were studied. APU composition with natural compounds increases their thermal stability both in air and in nitrogen atmosphere due to the formation of additional bonds between active groups of APU, protein and chrome tanning agent as the result of chemical reactions between organic and inorganic parts with the new structure formation.DOI: http://dx.doi.org/10.5755/j01.ms.22.3.10043

  6. The immobilization of anion exchange resins in polymer modified cements

    International Nuclear Information System (INIS)

    Dyer, A.; Morgan, P.D.

    1991-09-01

    Organic anion exchange resins, loaded with 99-Tc as the pertechnate ion, were incorporated into polymer modified cements (Flexocrete Ltd, Preston). BFS/OPC (9:1 mix) also was modified by three polymers from the same source (styrene acrylic (2) styrene butadiene) and loaded with anion exchanger containing the pertechnate. Composites were tested for initial compressive strengths, under water and radiation stability and leach rate. IAEA standard leach testing was with simulated sea and ground waters. Ground water leaching also was carried out on composites subjected to 1.10 9 rads (γ). Leach testing correlated well with compressive strength. Modified composites performed better than the BFS/OPC mix under all conditions studied and were able to encapsulate higher resin loadings. (author)

  7. Anionic lipids and the maintenance of membrane electrostatics in eukaryotes.

    Science.gov (United States)

    Platre, Matthieu Pierre; Jaillais, Yvon

    2017-02-01

    A wide range of signaling processes occurs at the cell surface through the reversible association of proteins from the cytosol to the plasma membrane. Some low abundant lipids are enriched at the membrane of specific compartments and thereby contribute to the identity of cell organelles by acting as biochemical landmarks. Lipids also influence membrane biophysical properties, which emerge as an important feature in specifying cellular territories. Such parameters are crucial for signal transduction and include lipid packing, membrane curvature and electrostatics. In particular, membrane electrostatics specifies the identity of the plasma membrane inner leaflet. Membrane surface charges are carried by anionic phospholipids, however the exact nature of the lipid(s) that powers the plasma membrane electrostatic field varies among eukaryotes and has been hotly debated during the last decade. Herein, we discuss the role of anionic lipids in setting up plasma membrane electrostatics and we compare similarities and differences that were found in different eukaryotic cells.

  8. Rejuvenation of the anion exchanger used for uranium recovery

    International Nuclear Information System (INIS)

    Yan, T.-Y.; Espenscheid, W.F.

    1986-01-01

    The present invention is directed to improving the performance of strong base anionic exchange resins used in uranium recovery that exhibit an undesirable decrease in loading capacity and in total exchange capacity. The invention comprises treating an anionic exchange resin to remove physically adsorbed and occluded fouling agents and to remove poisons which may be chemically bound to active ion groups on the resin. The process involves treating the resin, after the uranium ion exchange stage, with an alkaline carbonate solution, preferably treating the resin with an acid eluant first. The acid treatment dissolves insoluble fouling agents which are physically occluded or adsorbed by the resin and that the weak base treatment augments that result and probably removes poisons which are physically or chemically bound to the resin

  9. 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.

  10. Organic anion transporting polypeptide 1B transporters modulate hydroxyurea pharmacokinetics

    OpenAIRE

    Walker, Aisha L.; Lancaster, Cynthia S.; Finkelstein, David; Ware, Russell E.; Sparreboom, Alex

    2013-01-01

    Hydroxyurea is currently the only FDA-approved drug that ameliorates the pathophysiology of sickle cell anemia. Unfortunately, substantial interpatient variability in the pharmacokinetics (PK) of hydroxyurea may result in variation of the drug's efficacy. However, little is known about mechanisms that modulate hydroxyurea PK. Recent in vitro studies identifying hydroxyurea as a substrate for organic anion transporting polypeptide (OATP1B) transporters prompted the current investigation assess...

  11. 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

  12. Salts of alkali metal anions and process of preparing same

    Science.gov (United States)

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  13. Inorganic anion exchangers for the treatment of radioactive wastes

    International Nuclear Information System (INIS)

    Dyer, A.; Jamil, M.A.

    1987-07-01

    Inorganic anion exchangers are evaluated for Tc, I and S isotope removal from aqueous nuclear waste streams. Chemical, thermal, and radiation stabilities were examined. Selected exchangers were examined in detail for their selectivities, kinetics and mechanism of the sorption process (especially in NO 3 - , OH - and BO 3 - environments). Cement encapsulation and leaching experiments were made on the exchangers showing most promise for 'radwaste' treatment. (author)

  14. Organic resin anion exchangers for the treatment of radioactive wastes

    International Nuclear Information System (INIS)

    Dyer, A.; McGinnes, D.F.

    1988-07-01

    Organic anion exchange resins are evaluated for 99-TcO 4 - (pertechnate) removed from aqueous nuclear waste streams. Chemical, thermal and radiation stabilities were studied. Selected resins were examined in detail for their selectivities in the presence of I - , NO 3 - , SO 4 = , CO 3 = , Cl - and OH - . Ion exchange equilibria and kinetic mechanisms were determined. Preliminary investigations of cement encapsulation in polymer modified form were made and some leach studies carried out. (author)

  15. Closing anion gap without insulin in euglycaemic diabetic ketoacidosis

    Directory of Open Access Journals (Sweden)

    Resham Raj Poudel

    2017-01-01

    Full Text Available Euglycaemic diabetic ketoacidosis (euDKA occurs in patients with poor carbohydrate intake who continue to take insulin. For these patients are not truly in the insulin-deficient state, intravenous fluid resuscitation alone can correct the ketoacidosis without any risk of hypoglycaemia. Diagnosis of euDKA can be missed in inexperienced settings; therefore, calculating anion gap and measuring ketone levels should be practiced in every sick diabetic patient regardless of glucose levels.

  16. A novel nanostructured composite formed by interaction of copper octa(3-aminopropyl)octasilsesquioxane with azide ligands: Preparation, characterization and a voltammetric application

    International Nuclear Information System (INIS)

    Ribeiro do Carmo, Devaney; Paim, Leonardo Lataro; Metzker, Gustavo; Dias Filho, Newton Luiz; Stradiotto, Nelson Ramos

    2010-01-01

    This study presents the preparation, characterization and application of copper octa(3-aminopropyl)octasilsesquioxane following its subsequent reaction with azide ions (ASCA). The precursor (AC) and the novel compound (ASCA) were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), scanning electronic microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analyses and voltammetric technique. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E 1/2 ox ) = 0.30 V and an irreversible process at 1.1 V (vs. Ag/AgCl; NaCl 1.0 M; v=20mVs -1 ). The material is very sensitive to nitrite concentrations. The modified graphite paste electrode (GPE-ASCA) gives a linear range from 1.0 x 10 -4 to 4.0 x 10 -3 mol L -1 for the determination of nitrite, with a detection limit of 2.1 x 10 -4 mol L -1 and the amperometric sensitivity of 8.04 mA/mol L -1 .

  17. Studies on the rice seed (Oryza sativa) sensitivity to gama radiation, neutrons di-enthyl sulphate (DES) and sodium azide (SA)

    International Nuclear Information System (INIS)

    Guimaraes, E.P.

    1978-04-01

    Dry rice seeds of 'Dourado Precoce' variety were treated with gama-rays, thermal and fast neutrons, di-ethyl sulphate (DES) and sodium azide (SA). Biologial effects on survival, seedling height, plant fertility and chlorophy 11 mutation frequency were studied in the M 1 generation. The data obtained were analysed by 'independent test'. Survival was not affected by increased gama ray dosage, but by increased DES and SA dosages, as well as by SA treatments with increased solution acidity for seeds pretreated in distilled water. Seedling height was decreased with the increase of gama-ray dosage, DES concentration. SA acidity and concentration. Plant fertility was reduced drastically with higher gama-ray and neutron dosages and with high SA acidity and concentrations. The maximum chlorophy 11 mutation frequency was obtained in the SA treatment. Seeds pretreated with distilled water showed larger physiological damages in the SA treatments and higher mutation frequencies. Regarding chlorophyll mutation frequency, thermal neutrons were more efficient than gama-rays. SA was the most efficient mutagen used . DES showed lower physiological damages in the M 1 plants, but did not induce mutations in the used conditions [pt

  18. Chelator-Accelerated One-Pot ‘Click’ Labeling of Small Molecule Tracers with 2-[18F]Fluoroethyl Azide

    Directory of Open Access Journals (Sweden)

    Erik Årstad

    2013-05-01

    Full Text Available 2-[18F]Fluoroethyl azide ([18F]FEA can readily be obtained by nucleophilic substitution of 2-azidoethyl-4-toluenesulfonate with [18F]fluoride (half-life 110 min, and has become widely used as a reagent for ‘click’ labeling of PET tracers. However, distillation of [18F]FEA is typically required, which is time-consuming and unpractical for routine applications. In addition, copper(I-catalyzed cycloaddition of [18F]FEA with non-activated alkynes, and with substrates containing labile functional groups, can be challenging. Herein, we report a highly efficient and practical ligand-accelerated one-pot/two-step method for ‘click’ labeling of small molecule tracers with [18F]FEA. The method exploits the ability of the copper(I ligand bathophenanthrolinedisulfonate to accelerate the rate of the cycloaddition reaction. As a result, alkynes can be added directly to the crude reaction mixture containing [18F]FEA, and as cyclisation occurs almost immediately at room temperature, the reaction is tolerant to labile functional groups. The method was demonstrated by reacting [18F]FEA with a series of alkyne-functionalized 6-halopurines to give the corresponding triazoles in 55–76% analytical radiochemical yield.

  19. Divergent Pathways Involving 1,3-Dipolar Addition and N-N Bond Splitting of an Organic Azide across a Zirconium Methylidene.

    Science.gov (United States)

    Kurogi, Takashi; Mane, Manoj V; Zheng, Shuai; Carroll, Patrick J; Baik, Mu-Hyun; Mindiola, Daniel J

    2018-02-12

    The zirconium methylidene (PNP)Zr=CH 2 (OAr) (1) reacts with N 3 Ad to give two products (PNP)Zr=NAd(OAr) (2) and (PNP)Zr(η 2 -N=NAd)(N=CH 2 )(OAr) (3), both resulting from a common cycloaddition intermediate (PNP)Zr(CH 2 N 3 Ad)(OAr) (A). Using a series of control experiments in combination with DFT calculations, it was found that 2 results from a nitrene by a carbene metathesis reaction in which N 2 acts as a delivery vehicle and forms N 2 CH 2 as a side product. In the case of 3, N-N bond splitting of the azide at the α-position allowed the isolation of a rare example of a parent ketimide complex of zirconium. Isotopic labeling studies and solid-state X-ray analysis are presented for 2 and 3, in addition to an independent synthesis for the former. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Detection of sodium azide-induced mutagenicity in the regenerated shoots of artemisia annual L., using internal transcribed spacer (its) sequences of nrDNA

    International Nuclear Information System (INIS)

    Al-Qurainy, F.; Al-Hemaidi, F.M.; Khan, S.; Ali, M.A.; Tarroum, M.; Ashraf, M.

    2011-01-01

    Sodium azide (NaN/sub 3/) is a well known chemical mutagen which can effectively cause point mutation in plant genome. The mutagenicity by this potential mutagen was assessed in the regenerated mutant shoots of Artemisia annua using internal transcribed spacer (ITS) sequences of n rDNA. Insertions and/or deletions were detected in n rDNA-ITS sequences of all mutant shoots and compared with control ones using the ClustalX program. The regenerated shoots TS1 and TS2 had deleted bases, whereas TS3, TS4 and TS5 had insertions, because NaN/sub 3/ replaced the cytosine (C) by thymine (T) (C - T) (shoots; TS1 and TS4) and thymine (T) replaced by guanine (G) (T - G) (shoot; TS5), respectively. Artemisinin content was also measured in the regenerated six-week-old shoots of A. annua. All regenerated shoots had enhanced level of this compound as compared to that in the controls, being highest in the regenerated shoot TS3. (author)

  1. 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.

  2. Coumarin benzothiazole derivatives as chemosensors for cyanide anions

    Science.gov (United States)

    Wang, Kangnan; Liu, Zhiqiang; Guan, Ruifang; Cao, Duxia; Chen, Hongyu; Shan, Yanyan; Wu, Qianqian; Xu, Yongxiao

    2015-06-01

    Four coumarin benzothiazole derivatives, N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (1), (Z)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide (2), 7-(diethylamino)-N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (3) and (Z)-7-(diethylamino)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide) (4), have been synthesized. Their crystal structures, photophysical properties in acetonitrile and recognition properties for cyanide anions have been investigated. All the compounds are generally planar, especially compound 1 exhibits perfect planarity with dihedral angle between benzothiazolyl group and coumarin group being only 3.63°. Coumarin benzothiazole compounds 1 and 3 can recognize cyanide anions by Michael addition reaction and compound 3 exhibits color change from yellow to colorless and green fluorescence was quenched completely, which can be observed by naked eye. Coumarin benzothiazolyliden compound 4 can recognize cyanide anions with fluorescence turn-on response based on the copper complex ensemble displacement mechanism.

  3. Preparation and physicochemical characterization of anionic uranyl. beta. -ketoenolates

    Energy Technology Data Exchange (ETDEWEB)

    Marangoni, G; Paolucci, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Graziani, R; Celon, E

    1978-01-01

    New classes of anionic uranyl ..beta..-ketoenolates of formula (UO/sub 2/L/sub 2/X)/sup -/ (where L = 1,3-diphenylpropane-1,3-dionate (dppd), 4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfpbd), or 1-phenylbutane-1,3-dionate (pbd); X = Cl/sup -/, Br/sup -/, I/sup -/, (NO/sub 3/)/sup -/, (O/sub 2/CMe)/sup -/, or (NCS)/sup -/) and (L/sub 2/O/sub 2/U(..mu..-X) UO/sub 2/L/sub 2/)/sup -/ (where X = F/sup -/, and also Cl/sup -/ only in the case of L = dppd) have been synthesized and characterized by a number of physical measurements. The different ability of the various anionic ligands to enter into the co-ordination sphere of the uranyl ion, their potentially different bonding modes, and the possible correlations between physical parameters and the nature of either the chelate substituents or the anionic ligand are discussed.

  4. Demonstrate use of capillary electrophoresis low level transient of anions

    International Nuclear Information System (INIS)

    Moum, Kari-Lye; Solheim, Torill; McElrath, Joel; Frattini, Paul

    2012-09-01

    Capillary Electrophoresis (CE) is a well-known analytical method capable of rapid detection of very low concentration of cations and anionic species such as chloride, sulfate and nitrate. These anions are of crucial importance in reducing the potential of stainless steel components to undergo stress corrosion cracking. Currently, Nuclear Power Plants (NPPs) use Ion Chromatography (IC) as the analytical technique to achieve the required detection levels of ionic species. At the Halden Reactor Project (HRP) IC was replaced by CE in 1996, and since then HRP has gained nearly 20 years of operational experience. During the last 15 years, EPRI has done research on the CE technique and has achieved extensive experience in this area. EPRI has demonstrated detection levels at ppt and sub-ppb levels. This paper presents the ability of the CE technique to follow low level transients of anions in Boiling Water Reactor (BWR) coolant. A transient caused by approx. 10 ppb chloride and sulfate was simulated in an experimental circuit simulating BWR conditions. A series of grab samples were taken and analysed using HRPs CE (Agilent G1600). (authors)

  5. 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.

  6. 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.

  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

    2016-11-01

    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.

  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

    2016-01-01

    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

  9. 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.

  10. 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.

  11. 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.

  12. Adsorption and desorption dynamics of citric acid anions in soil

    KAUST Repository

    Oburger, E.

    2011-07-26

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal uptake. Little is known about the interaction dynamics of organic acid anions with the soil matrix and the potential impact of adsorption and desorption processes on the functional significance of these effects. The aim of this study was to characterize experimentally the adsorption and desorption dynamics of organic acid anions in five agricultural soils differing in iron and aluminium oxide contents and using citrate as a model carboxylate. Results showed that both adsorption and desorption processes were fast in all soils, reaching a steady state within approximately 1 hour. However, for a given total soil citrate concentration (ct) the steady state was critically dependent on the starting conditions of the experiment, whether most of the citrate was initially present in solution (cl) or held on the solid phase (cs). Specifically, desorption-led processes resulted in significantly smaller steady-state solution concentrations than adsorption-led processes, indicating that hysteresis occurred. As it is not possible to distinguish between different adsorption and desorption pools in soil experimentally, a new dynamic hysteresis model that relies only on measured soil solution concentrations was developed. The model satisfactorily explained experimental data and was able to predict dynamic adsorption and desorption behaviour. To demonstrate its use, we applied the model to two relevant situations involving exudation and microbial degradation. The study highlighted the complex nature of citrate adsorption and desorption dynamics in soil. We conclude that existing models need to incorporate both temporal and hysteresis components to describe realistically the role and fate of organic acids in soil processes. © 2011 The

  13. Natural minerals and synthetic materials for sorption of radioactive anions

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Mun Ja; Chun, Kwan Sik; Kim, Seung Soo

    1998-07-01

    Technetium-99 and iodine-129 are fission products with long half-lives, and exist as highly soluble anionic species. Studies on natural and synthetic materials sorbing TcO{sub 4} and/or I have been performed by several researchers. The application of these materials as an additive in the high-level waste disposal has been considered. The iron- or sulfide-containing minerals such as metal iron, iron powder, stibnite and pyrrhotite show a high capacity for TcO{sub 4} sorption. And the small amounts of activated carbon are reported to have high distribution coefficients recently. In the iodine sorption studies, sulfide-, copper-, lead- or mercury-containing minerals can be a candidate. Pyrite, chalcopyrite, galena, Cu{sub 2}S and CuS reveal a high capacity for I sorption. The synthetic materials were found to have high sorption capacity and compensate the defects of natural minerals, which contain hydrous oxides such as zirconium oxide, aluminium oxide and mercarbide. The mercarbide has the high distribution coefficients for the sorption of TcO{sub 4} and I. Recently it was proposed that the synthetic clay, hydrotalcite, could be useful for the fixation of anion. However, to determine the applicability of those natural and synthetic materials as an additive to a buffer or backfill material for sorption of TcO{sub 4} and/or I, the sorption behavior of the anions on those materials under the repository conditions should be identified. (author). 32 refs., 21 tabs., 10 figs

  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. Detection of nearest neighbors to specific fluorescently tagged ligands in rod outer segment and lymphocyte plasma membranes by photosensitization of 5-iodonaphthyl 1-azide

    International Nuclear Information System (INIS)

    Raviv, Y.; Bercovici, T.; Gitler, C.; Salomon, Y.

    1989-01-01

    Lima bean agglutinin-fluorescein 5-isothiocyanate conjugate (FluNCS-lima bean lectin) interacts with specific receptor molecules on membranes both from the rod outer segment (ROS) of the frog retina and from S49 mouse lymphoma cells. When [125I]-5-iodonaphthyl 1-azide (125I-INA), which freely and randomly partitions into the lipid bilayer, is added to membranes and the suspension is irradiated at 480 nm, the FluNCS-conjugated lectin photosensitizes the [125I]INA but only at discrete sites. This results in the selective labeling of specific proteins: an 88-kDa protein on ROS membranes and a 56-kDa protein on S49 plasma membranes. Labeling is dependent upon the interaction of the FluNCS-lectin with glycosylated receptor sites, since N-acetylgalactosamine, but not methyl alpha-mannoside, blocked labeling of the 56-kDa protein on S49 membranes. In contrast, a random labeling pattern of membrane proteins was observed upon irradiation at 480 nm using other fluorescein conjugates, such as FluNCS-bovine serum albumin (FluNCS-BSA) or FluNCS-soybean trypsin inhibitor (FluNCS-STI), which interact with cell membranes in a nonselective manner, or with N-(fluorescein-5-thiocarbamoyl)-n-undecyclamine (FluNCS-NHC11), which is freely miscible in the membrane lipid. Random labeling was also obtained by direct photoexcitation of [125I]INA at 314 nm, with no distinct labeling of the 88- and 56-kDa proteins in the respective membranes. These results suggest that protein ligands can be used to guide sensitizers to discrete receptor sites and lead to their selective labeling by photosensitized activation of [125I]INA

  16. Purification, crystallization and preliminary X-ray crystallographic analysis of the ATPase domain of human TAP in nucleotide-free and ADP-, vanadate- and azide-complexed forms

    International Nuclear Information System (INIS)

    Meena, Sita R.; Gangwar, Shanti P.; Saxena, Ajay K.

    2012-01-01

    The ATPase domain of human TAP in nucleotide free, ADP, vanadate and azide complexed forms were purified and crystallized. The X-ray diffraction data sets were collected for all crystals in the resolution range of 2.8–3.0 Å. The human transporter associated with antigen processing (TAP) protein belongs to the ATP-binding cassette (ABC) transporter superfamily and is formed by the heterodimerization of TAP1 and TAP2 subunits. TAP selectively pumps cytosolic peptides into the lumen of the endoplasmic reticulum in an ATP-dependent manner. The catalytic cycle of the ATPase domain of TAP is not understood at the molecular level. The structures of catalytic intermediates of the ATPase domain of TAP will contribute to the understanding of the chemical mechanism of ATP hydrolysis. In order to understand this mechanism, the ATPase domain of human TAP1 (NBD1) was expressed and purified, crystallized in nucleotide-free and transition-state complex forms and X-ray crystallographic studies were performed. The NBD1 protein was crystallized (i) in the nucleotide-free apo form; (ii) in complex with ADP–Mg 2+ , mimicking the product-bound state; (iii) in complex with vanadate–ADP–Mg 2+ , mimicking the ATP-bound state; and (iv) in complex with azide–ADP–Mg 2+ , also mimicking the ATP-bound state. X-ray diffraction data sets were collected for apo and complexed NBD1 using an in-house X-ray diffraction facility at a wavelength of 1.5418 Å. The apo and complexed NBD1 crystals belonged to the primitive hexagonal space group P6 2 , with one monomer in the asymmetric unit. Here, the crystallization, data collection and preliminary crystallographic analysis of apo and complexed NBD1 are reported

  17. Fully recoverable rigid shape memory foam based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) using a salt leaching technique.

    Science.gov (United States)

    Alzahrani, Abeer A; Saed, Mohand; Yakacki, Christopher M; Song, Han Byul; Sowan, Nancy; Walston, Joshua J; Shah, Parag K; McBride, Matthew K; Stansbury, Jeffrey W; Bowman, Christopher N

    2018-01-07

    This study is the first to employ the use of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization to form a tough and stiff, porous material from a well-defined network possessing a high glass transition temperature. The effect of the network linkages formed as a product of the CuAAC reaction, i.e., the triazoles, on the mechanical behavior at high strain was evaluated by comparing the CuAAC foam to an epoxy-amine-based foam, which consisted of monomers with similar backbone structures and mechanical properties (i.e., T g of 115 °C and a rubbery modulus of 1.0 MPa for the CuAAC foam, T g of 125 °C and a rubbery modulus of 1.2 MPa for the epoxy-amine foam). When each foam was compressed uniformly to 80% strain at ambient temperature, the epoxy-amine foam was severely damaged after only reaching 70% strain in the first compression cycle with a toughness of 300 MJ/m 3 . In contrast, the CuAAC foam exhibited pronounced ductile behavior in the glassy state with three times higher toughness of 850 MJ/m 3 after the first cycle of compression to 80% strain. Additionally, when the CuAAC foam was heated above T g after each of five compression cycles to 80% strain at ambient temperature, the foam completely recovered its original shape while exhibiting a gradual decrease in mechanical performance over the multiple compression cycles. The foam demonstrated almost complete shape fixity and recovery ratios even through five successive cycles, indicative of "reversible plasticity", making it highly desirable as a glassy shape memory foams.

  18. Fixation of metallic sulfosalicylate complexes on an anionic exchange resin

    International Nuclear Information System (INIS)

    Cahuzac, S.

    1969-06-01

    Since sulfosalicylate ions have acid-base properties, sulfosalicylate complexes have an apparent stability which varies with the ph. As a result, the fixation of sulfo-salicylates on an anionic exchange resin depends on the ph of the solution in equilibrium with the resin. This research has been aimed at studying the influence of the ph on the fixation on an anionic exchange resin (Dowex 1 x 4) of sulfosalicylate anions on the one hand, and of metallic sulfosalicylate complexes on the other hand. In the first part of this work, a determination has been made, by frontal analysis of the distribution of sulfosalicylate ions in the resin according to the total sulfosalicylate I concentration in the aqueous solution in equilibrium with the resin. The exchange constants of these ions between the resin and the solution have been calculated. In the second part, a study has been made of the fixation of anionic sulfosalicylate complexes of Fe(III), Al(III), Cr(III), Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(II) and UO 2 2+ . By measuring the partition coefficients of these different elements between the resin and the solution it has been possible to give interpretation for the modes of fixation of the metallic ions, and to calculate their exchange constant between the resin and the solution. The relationship has been established for each metallic element studied, between its partition coefficient, the ph and the total concentration of the complexing agent in solution. Such a relationship makes it possible to predict, for given conditions, the nature of the species in solution and in the resin, as well as the partition coefficient of a metallic, element. Finally, in the third part of the work, use has been made of results obtained previously, to carry out some separations (Ni 2+ - Co 2+ ; Ni 2+ - Co 2+ - Cu 2+ ; UO 2 2+ - Fe 3+ ; UO 2 2+ - Cr 3+ ; UO 2 2+ - Cu 2+ ; UO 2 2+ - Ni 2+ ; UO 2 2+ - Co 2+ ; UO 2 2+ - Mn 2+ and UO 2 2+ - Cd 2+ ), as well as the purification

  19. On the Adsorption of Some Anionic Collectors on Fluoride Minerals

    DEFF Research Database (Denmark)

    Sørensen, Emil

    1973-01-01

    Test flotations have been carried out in a small apparatus under standardized conditions in order to determine the dependence of the flotation yield on the reagent concentration for certain minerals and anionic collectors. The results suggest that a special adsorption mechanism is operating...... in the case of fluoride minerals, and a theory is presented which involves the joint action of ionic and hydrogen bonds. A precondition is the compatibility of the crystal geometry with the configuration of the polar group of the collector molecules....

  20. Review: equipment for anionic surfactant manufacture from oil palm

    Directory of Open Access Journals (Sweden)

    Jesús Alfonso Torres Ortega

    2010-05-01

    Full Text Available In the present study is performed a review of the current processes of sulfonation of various raw materials for determine the process conditions in order to present the state of the art of sulfonation processes for the manufacture of anionic surfactants. There has been a scientific literature with emphasis on several aspects: Technology, sulfonation reactors and operating conditions in the process, analytical techniques for monitoring the reaction degree, the mathematical models proposed in the literature for the sulfonation/sulfation in tubular absorbers, patenting and specialized industry publications in this area.

  1. Quenching of p-Cyanophenylalanine Fluorescence by Various Anions.

    Science.gov (United States)

    Pazos, Ileana M; Roesch, Rachel M; Gai, Feng

    2013-03-20

    To expand the spectroscopic utility of the non-natural amino acid p -cyanophenylalanine (Phe CN ), we examine the quenching efficiencies of a series of commonly encountered anions toward its fluorescence. We find that iodide exhibits an unusually large Stern-Volmer quenching constant, making it a convenient choice in Phe CN fluorescence quenching studies. Indeed, using the villin headpiece subdomain as a testbed we demonstrate that iodide quenching of Phe CN fluorescence offers a convenient means to reveal protein conformational heterogeneity. Furthermore, we show that the amino group of Phe CN strongly quenches its fluorescence, suggesting that Phe CN could be used as a local pH sensor.

  2. Minority anion substitution by Ni in ZnO

    CERN Document Server

    Pereira, Lino Miguel da Costa; Correia, João Guilherme; Amorim, Lígia Marina; Silva, Daniel José; David-Bosne, Eric; Decoster, Stefan; da Silva, Manuel Ribeiro; Temst, Kristiaan; Vantomme, André

    2013-01-01

    We report on the lattice location of implanted Ni in ZnO using the $\\beta$− emission channeling technique. In addition to the majority substituting for the cation (Zn), a significant fraction of the Ni atoms occupy anion (O) sites. Since Ni is chemically more similar to Zn than it is to O, the observed O substitution is rather puzzling. We discuss these findings with respect to the general understanding of lattice location of dopants in compound semiconductors. In particular, we discuss potential implications on the magnetic behavior of transition metal doped dilute magnetic semiconductors.

  3. Molecular Recognition: Preparation and Characterization of Two Tripodal Anion Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Shokri, Alireza; Deng, Shihu; Wang, Xue B.; Kass, Steven R.

    2014-03-01

    Two new tripodal hydroxyl-based anion receptors (1 and 2) are reported and their molecular complexes with Cl–, H2PO4 –, and OAc– along with the (M–1)– ion of 1 were characterized by negative ion photoelectron spectroscopy in the gas phase and by binding constant determinations in four solvents (i.e., CDCl3, CD2Cl2, CD3COCD3, and CD3CN). An intramolecular hydrogen bond network (HBN) in hexaol 1 was found to diminish its binding whereas the triol 2 is the strongest aliphatic hydroxyl-based receptor to date.

  4. Registration of interstitial anions in irradiated MgO crystals

    International Nuclear Information System (INIS)

    Surzhikov, A.P.; Pogrebnyak, A.D.

    1985-01-01

    Possibility of application of positron annihilation for detection in oxides of rare earth metals with interstitial component of Frenkel anion defects is revealed. Magnesium oxide monocrystals with Ca, Si, Fe, Al impurity contents of 0.1 wt.% were investigated. These crystals were irradiated by X-rays (45 kV, 20 μA) and protons (10 MeV). It is shown that heating of magnesium oxide crystals irradiated by protons up to 700 K completely anneals F + -centers. In this case the component disappears inth the pulse distributon at xi=5.0; the subsequent crystal irradiation with X-ray does not lead to its reduction

  5. Separation of boron isotopes using NMG type anion exchange resin

    International Nuclear Information System (INIS)

    Itagaki, Takaharu; Kosuge, Masao; Fukuda, Junji; Fujii, Yasuhiko.

    1992-01-01

    Ion exchange separation of boron isotopes (B-10 and B-11) has been studied by using a special boron selective ion exchange resin; NMG (n-methyl glucamine)-type anion exchange resin. The resin has shown a large isotope separation coefficient of 1.02 at the experimental conditions of temperature, 80degC, and boric acid concentration, 0.2 M (mole/dm 3 ). Enriched B-10 (92%) was obtained after the migration of 1149 m by a recyclic operation of ion exchange columns in a merry-go-round method. (author)

  6. 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.

  7. Review of cell performance in anion exchange membrane fuel cells

    Science.gov (United States)

    Dekel, Dario R.

    2018-01-01

    Anion exchange membrane fuel cells (AEMFCs) have recently received increasing attention since in principle they allow for the use of non-precious metal catalysts, which dramatically reduces the cost per kilowatt of power in fuel cell devices. Until not long ago, the main barrier in the development of AEMFCs was the availability of highly conductive anion exchange membranes (AEMs); however, improvements on this front in the past decade show that newly developed AEMs have already reached high levels of conductivity, leading to satisfactory cell performance. In recent years, a growing number of research studies have reported AEMFC performance results. In the last three years, new records in performance were achieved. Most of the literature reporting cell performance is based on hydrogen-AEMFCs, although an increasing number of studies have also reported the use of fuels others than hydrogen - such as alcohols, non-alcohol C-based fuels, as well as N-based fuels. This article reviews the cell performance and performance stability achieved in AEMFCs through the years since the first reports in the early 2000s.

  8. Dynamics of anion-molecule reactions at low energy

    International Nuclear Information System (INIS)

    Mikosch, J.

    2007-11-01

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

  9. Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions.

    Science.gov (United States)

    Martins, Vitor L; Rennie, Anthony J R; Sanchez-Ramirez, Nedher; Torresi, Roberto M; Hall, Peter J

    2018-02-01

    Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN) 4 ] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm -1 ). Herein, we report the use of ILs containing the [B(CN) 4 ] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two-electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g -1 @ 15 A g -1 ). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs.

  10. Diffusion of anions and cations in compacted sodium bentonite

    International Nuclear Information System (INIS)

    Muurinen, A.

    1994-02-01

    The thesis presents the results of studies on the diffusion mechanisms of anions and cations in compacted sodium bentonite, which is planned to be used as a buffer material in nuclear waste disposal in Finland. The diffusivities and sorption factors were determined by tracer experiments. The pore volume accessible to chloride, here defined as effective porosity, was determined as a function of bentonite density and electrolyte concentration in water, and the Stern-Gouy double-layer model was used to explain the observed anion exclusion. The sorption of Cs + and Sr 2+ was studied in loose and compacted bentonite samples as a function of the electrolyte concentration in solution. In order to obtain evidence of the diffusion of exchangeable cations, defined as surface diffusion, the diffusivities of Cs + and Sr 2+ in compacted bentonite were studied as a function of the sorption factor, which was varied by electrolyte concentration in solution. The measurements were performed both by a non-steady state method and by a through-diffusion method. (89 refs., 35 fig., 4 tab.)

  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. Cation-enhanced capillary electrophoresis separation of atropoisomer anions.

    Science.gov (United States)

    Na, Yun-Cheol; Berthod, Alain; Armstrong, Daniel W

    2015-12-01

    CE was used to study the separation of the atropoisomers of four phosphoric acids and two sulfonic acids and the enantiomers of two phosphoric acids. All solutes are in their anionic forms in aqueous electrolytes. The chiral additives were two hydroxypropyl cyclodextrins (CDs) and cyclofructan 6 (CF6). The CDs were able to separate four solutes and the CF6 additive could separate only one: 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BHP). Since CF6 is able to bind with cations, nitrate of alkaline metals, Ba(2+) , and Pb(2+) were added, greatly improving the BHP separation at the expense of longer migration times. There seems to be a link between CF6-cation-binding constants and BHP resolution factors. Cation additions were also performed with CD selectors that are less prone to form complexes with cations. Significant improvements of enantiomer or atropoisomer separations were observed also associated with longer migration times. It is speculated that the anionic solutes associate with the added cations forming larger entities better differentiated by CDs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthetic cation-selective nanotube: permeant cations chaperoned by anions.

    Science.gov (United States)

    Hilder, Tamsyn A; Gordon, Dan; Chung, Shin-Ho

    2011-01-28

    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  14. Dynamics of anion-molecule reactions at low energy

    Energy Technology Data Exchange (ETDEWEB)

    Mikosch, J.

    2007-11-15

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

  15. 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)

  16. 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.

  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. 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.

  19. 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...

  20. Removal of 125I from radioactive experimental waste with an anion exchange paper membrane

    International Nuclear Information System (INIS)

    Inoue, Hiroyoshi; Kagoshima, Mayumi

    2000-01-01

    The behavior of radioactive iodide and chloride ions through an anion exchange paper membrane to remove 125 I from radioactive experimental waste has been studied with nonequilibrium thermodynamic analyses. Anion exchange paper membrane was found to be electroconductively more permeable to iodide ion than to chloride ion. The iodide ion bound more strongly to the anion exchange site within a membrane phase than the chloride ion by more than twice. The results suggested that an anion exchange paper membrane was appropriate for the filtration removal system

  1. 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

  2. Migratory Insertion of Hydrogen Isocyanide in the Pentacyano(methyl)cobaltate(III) Anion

    DEFF Research Database (Denmark)

    Kofod, Pauli; Harris, Pernille Hanne; Larsen, Sine

    2003-01-01

    The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been spectrosco......The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been...

  3. Anionic 11-mercaptoundecanoic acid capped ZnO nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Šimšíková, Michaela, E-mail: michaela.simsikova@ceitec.vutbr.cz [CEITEC BUT, Brno University of Technology, Technická 10, 616 69 Brno (Czech Republic); Antalík, Marián [Department of Biochemistry, Faculty of Science, P.J. Šafárik University, Šrobárova 2, 041 54 Košice (Slovakia); Department of Biophysics, Institute of Experimental Physics, SAS, Watsonova 47, 040 01 Košice (Slovakia); Kaňuchová, Mária; Škvarla, Jiří [Institute of Montaneous Sciences and Environmental Protection, Faculty of Mining, Ecology, Process Control and Geotechnologies, Technical University of Košice, Park Komenského 19, 043 84 Košice (Slovakia)

    2013-10-01

    The anionic zinc oxide nanoparticles have been prepared at room temperature by a precipitation method using ZnCl{sub 2} and NaOH and surface modification with 11-mercaptoundecanoic acid (MUA). Atomic force microscopy (AFM) was used for definition of morphology and size of prepared nanoparticles which was proved by measurements of particle size distribution using Zetasizer. Successful coating with MUA as surfactant was acknowledged by X-ray photoelectron spectroscopy and ATR FT-IR spectroscopy. The isoelectric point (IEP) of ZnO–MUA nanoparticles was obtained by measurements of zeta potential and FT-IR dependence on pH; the obtained value was approximately 3.58. The value of exchanged protons was 2.88 which indicates a positive binding cooperativity of modified nanoparticles.

  4. 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.

  5. Partial molar volume of anionic polyelectrolytes in aqueous solution.

    Science.gov (United States)

    Salamanca, Constain; Contreras, Martín; Gamboa, Consuelo

    2007-05-15

    In this work the partial molar volumes (V) of different anionic polyelectrolytes and hydrophobically modified polyelectrolytes (PHM) were measured. Polymers like polymaleic acid-co-styrene, polymaleic acid-co-1-olefin, polymaleic acid-co-vinyl-2-pyrrolidone, and polyacrylic acid (abbreviated as MAS-n, PA-n-K2, AMVP, and PAA, respectively) were employed. These materials were investigated by density measurements in highly dilute aqueous solutions. The molar volume results allow us to discuss the effect of the carboxylic groups and the contributions from the comonomeric principal chain. The PAA presents the smaller V, while the largest V value was for AMVP. The V of PHM shows a linear relationship with the number of methylene groups in the lateral chain. It is found that the magnitude of the contribution per methylene group decreases as the hydrophobic character of the environment increases.

  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. Using solvent extraction to process nitrate anion exchange column effluents

    International Nuclear Information System (INIS)

    Yarbro, S.L.

    1987-10-01

    Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), a new organophosphorous extractant, and a new centrifugal mixer-settler both recently developed at Argonne were evaluated for their potential use in the recovery of actinides from nitrate anion exchange column effluents. The performance of the extractant was evaluated by measuring the extraction coefficient values as a function of acid and salt concentration. Additional performance parameters include extraction coefficient behavior as a function of the total metal concentration in the organic phase, and comparison of different stripping and organic scrubbing techniques. A simulated effluent stream was used to evaluate the performance of the centrifugal mixer-settlers by comparing experimental and calculated interstage concentration profiles. Both the CMPO extractant and the centrifugal mixer-settlers have potential for processing nitrate column effluents, particularly if the stripping behavior can be improved. Details of the proposed process are presented in the flowsheet and contactor design analyses

  8. Using solvent extraction to process nitrate anion exchange column effluents

    Energy Technology Data Exchange (ETDEWEB)

    Yarbro, S.L.

    1987-10-01

    Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), a new organophosphorous extractant, and a new centrifugal mixer-settler both recently developed at Argonne were evaluated for their potential use in the recovery of actinides from nitrate anion exchange column effluents. The performance of the extractant was evaluated by measuring the extraction coefficient values as a function of acid and salt concentration. Additional performance parameters include extraction coefficient behavior as a function of the total metal concentration in the organic phase, and comparison of different stripping and organic scrubbing techniques. A simulated effluent stream was used to evaluate the performance of the centrifugal mixer-settlers by comparing experimental and calculated interstage concentration profiles. Both the CMPO extractant and the centrifugal mixer-settlers have potential for processing nitrate column effluents, particularly if the stripping behavior can be improved. Details of the proposed process are presented in the flowsheet and contactor design analyses.

  9. 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.

  10. Reactivity of amino acid anions with nitrogen and oxygen atoms.

    Science.gov (United States)

    Wang, Zhe-Chen; Li, Ya-Ke; He, Sheng-Gui; Bierbaum, Veronica M

    2018-02-14

    For many decades, astronomers have searched for biological molecules, including amino acids, in the interstellar medium; this endeavor is important for investigating the hypothesis of the origin of life from space. The space environment is complex and atomic species, such as nitrogen and oxygen atoms, are widely distributed. In this work, the reactions of eight typical deprotonated amino acids (glycine, alanine, cysteine, proline, aspartic acid, histidine, tyrosine, and tryptophan) with ground state nitrogen and oxygen atoms are studied by experiment and theory. These amino acid anions do not react with nitrogen atoms. However, the reactions of these ions with oxygen atoms show an intriguing variety of ionic products and the reaction rate constants are of the order of 10 -10 cm 3 s -1 . Density functional calculations provide detailed mechanisms of the reactions, and demonstrate that spin conversion is essential for some processes. Our study provides important data and insights for understanding the kinetic and dynamic behavior of amino acids in space environments.

  11. Preliminary Testing For Anionic, Cationic and Non-ionic

    Directory of Open Access Journals (Sweden)

    Bokic, Lj.

    2007-11-01

    Full Text Available Detergents present a major environmental problem due to large quantities of surfactants released from laundries. For this reason, it is important to apply an appropriate analytical method for their determination. In this work, we propose two simple, fast and inexpensive analytical methods for anionic, cationic and non-ionic surfactant determination: thin layer chromatography (TLC separation for qualitative screening and quantitative potentiometric determination with ion-selective electrodes. These methods have been chosen because of their many advantages: rapidity, ease of operation, low cost of analysis and a wide variety of TLC application possibilities. The advantage of potentiometric titration is its very high degree of automation and very low detection limits obtained with different ion-selective electrodes applied for different surfactants.

  12. Common, yet elusive: a case of severe anion gap acidosis.

    Science.gov (United States)

    Agrawal, Akanksha; Kishlyansky, Marina; Biso, Sylvia; Patnaik, Soumya; Punjabi, Chitra

    2017-09-01

    Acid-base disturbances are common occurrence in hospitalized patients with life threatening complications. 5-oxoproline has been increasingly recognized as cause of high anion gap metabolic acidosis (AGMA) in association with chronic acetaminophen use. However, laboratory workup for it are not widely available. We report case of 56-year-old female with severe AGMA not attributable to ketoacidosis, lactic acidosis or toxic ingestion. History was significant for chronic acetaminophen use, and laboratory workup negative for all frequent causes of AGMA. Given history and clinical presentation, our suspicion for 5-oxoproline toxicity was high. Our patient required emergent hemodialysis and subsequently improved clinically. With an increasing awareness of the uncommon causes of high AGMA, tests should be more readily available to detect their presence. Physicians should be more vigilant of underdiagnosed causes of AGMA if the presentation and laboratory values do not reflect a common cause, as definitive treatment may vary based on the offending agent.

  13. Removal of both cationic and anionic contaminants by amphoteric starch.

    Science.gov (United States)

    Peng, Huanlong; Zhong, Songxiong; Lin, Qintie; Yao, Xiaosheng; Liang, Zhuoying; Yang, Muqun; Yin, Guangcai; Liu, Qianjun; He, Hongfei

    2016-03-15

    A novel amphoteric starch incorporating quaternary ammonium and phosphate groups was applied to investigate the efficiency and mechanism of cationic and anionic contaminant treatment. Its flocculation abilities for kaolin suspension and copper-containing wastewater were evaluated by turbidity reduction and copper removal efficiency, respectively. And the kinetics of formation, breakage and subsequent re-formation of aggregates were monitored using a Photometric Dispersion Analyzer (PDA) and characterized by flocculation index (FI). The results showed that amphoteric starch possessed the advantages of being lower-dosages-consuming and being stronger in shear resistance than cationic starch, and exhibited a good flocculation efficiency over a wide pH range from 3.0 to 11.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Enhanced DOC removal using anion and cation ion exchange resins.

    Science.gov (United States)

    Arias-Paic, Miguel; Cawley, Kaelin M; Byg, Steve; Rosario-Ortiz, Fernando L

    2016-01-01

    Hardness and DOC removal in a single ion exchange unit operation allows for less infrastructure, is advantageous for process operation and depending on the water source, could enhance anion exchange resin removal of dissolved organic carbon (DOC). Simultaneous application of cationic (Plus) and anionic (MIEX) ion exchange resin in a single contact vessel was tested at pilot and bench scales, under multiple regeneration cycles. Hardness removal correlated with theoretical predictions; where measured hardness was between 88 and 98% of the predicted value. Comparing bench scale DOC removal of solely treating water with MIEX compared to Plus and MIEX treated water showed an enhanced DOC removal, where removal was increased from 0.5 to 1.25 mg/L for the simultaneous resin application compared to solely applying MIEX resin. A full scale MIEX treatment plant (14.5 MGD) reduced raw water DOC from 13.7 mg/L to 4.90 mg/L in the treated effluent at a bed volume (BV) treatment rate of 800, where a parallel operation of a simultaneous MIEX and Plus resin pilot (10 gpm) measured effluent DOC concentrations of no greater than 3.4 mg/L, even at bed volumes of treatment 37.5% greater than the full scale plant. MIEX effluent compared to simultaneous Plus and MIEX effluent resulted in differences in fluorescence intensity that correlated to decreases in DOC concentration. The simultaneous treatment of Plus and MIEX resin produced water with predominantly microbial character, indicating the enhanced DOC removal was principally due to increased removal of terrestrially derived organic matter. The addition of Plus resin to a process train with MIEX resin allows for one treatment process to remove both DOC and hardness, where a single brine waste stream can be sent to sewer at a full-scale plant, completely removing lime chemical addition and sludge waste disposal for precipitative softening processes. Published by Elsevier Ltd.

  15. 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.

  16. 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.

  17. Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions

    NARCIS (Netherlands)

    Dain, R. P.; Leavitt, C. M.; Oomens, J.; Steill, J. D.; Groenewold, G. S.; van Stipdonk, M. J.

    2010-01-01

    The structures of gas-phase, metal chlorate anions with the formula [M(ClO3)(2)](-), M = Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental

  18. 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.

  19. Facilitated transport of hydrophilic salts by mixtures of anion and cation carriers and by ditopic carriers

    NARCIS (Netherlands)

    Chrisstoffels, L.A.J.; de Jong, Feike; Reinhoudt, David; Sivelli, Stefano; Gazzola, Licia; Casnati, Alessandro; Ungaro, Rocco

    1999-01-01

    Anion transfer to the membrane phase affects the extraction efficiency of salt transport by cation carriers 1 and 3. Addition of anion receptors 5 or 6 to cation carriers 1, 3, or 4 in the membrane phase enhances the transport of salts under conditions in which the cation carriers alone do not

  20. 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.

  1. Supramolecular binding and release of sulfide and hydrosulfide anions in water.

    Science.gov (United States)

    Vázquez, J; Sindelar, V

    2018-06-05

    Hydrogen sulfide (H2S) has become an important target for research due to its physiological properties as well as its potential applications in medicine. In this work, supramolecular binding of sulfide (S2-) and hydrosulfide (HS-) anions in water is presented for the first time. Bambusurils were used to slow down the release of these anions in water.

  2. Anionic polymerization and polyhomologation: An ideal combination to synthesize polyethylene-based block copolymers

    KAUST Repository

    Zhang, H.

    2013-08-07

    A novel one-pot methodology combining anionic polymerization and polyhomologation, through a "bridge" molecule (BF3OEt 2), was developed for the synthesis of polyethylene (PE)-based block copolymers. The anionically synthesized macroanion reacts with the "bridge" molecule to afford a 3-arm star (trimacromolecular borane) which serves as an initiator for the polyhomologation. 2013 The Royal Society of Chemistry.

  3. 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

  4. Analysing destruction channels of interstellar hydrocarbon anions with a 22pol ion-trap

    Energy Technology Data Exchange (ETDEWEB)

    Endres, Eric; Lakhmanskaya, Olga; Best, Thorsten; Hauser, Daniel; Kumar, Sunil; Wester, Roland [Universitaet Innsbruck, Institut fuer Ionenphysik und Angewandte Physik (Austria)

    2014-07-01

    In the interstellar medium (ISM), ion-molecule reactions are considered to play a key role in the formation of complex molecules. The detection of the first interstellar anions, which happen to be carbon chain anions, has raised new interest in the quantitative composition of the ISM and the underlying reaction network. To understand the observed abundance of these carbon chain anions, a detailed analysis of the possible destruction channels is indispensable. A cryogenic 22-pol radio frequency ion trap is an ideal tool to observe reactions that take place slowly, such as carbon chain anions with molecular hydrogen. Furthermore, measurements over a large temperature scale are feasible. Longitudinal optical access to the trap also provides the possibility to make precise photodetachment measurements. Temperature dependent measurements of the reaction rates for the reaction between hydrocarbon chain anions and H{sub 2} are presented.

  5. A procedure for reducing the concentration of hydrogen ions in acid anionic eluate and equipment therefore

    International Nuclear Information System (INIS)

    Parobek, P.; Baloun, S.; Plevac, S.

    1989-01-01

    The method is described of reducing the concentration of hydrogen ions in acid anionic eluate produced in the separation of uranium or other metals, in which anion exchanger elution, precipitation, filtration and precipitate and anion exchanger washing are used. The technological line for such elution comprises at least one ion exchange column and at least one container. They together form the first and the second stages of preparation of the acid anion elution solution, the sorption-elution separation of hydrogen ions on an cation exchanger being inserted between them. The preparation of the solution is divide into two stages. In the first stage, the acid and part of the solution for the preparation of the acid anion elution solution are supplied. The resulting enriched acid elution solution is fe onto the cation exchanger where the hydrogen ion concentration i reduced. It is then carried into the second stage where it is mixed with the remaining part of the solution. (B.S.)

  6. Physical Removal of Anions from Aqueous Media by Means of a Macrocycle-Containing Polymeric Network

    KAUST Repository

    Ji, Xiaofan

    2018-02-13

    Reported here is a hydrogel-forming polymer network that contains a water-soluble tetracationic macrocycle. Upon immersion of this polymer network in aqueous solutions containing various inorganic and organic salts, changes in the physical properties are observed that are consistent with absorption of the constituent anions into the polymer network. This absorption is ascribed to host-guest interactions involving the tetracationic macrocyclic receptor. Removal of the anions may then be achieved by lifting the resulting hydrogels out of the aqueous phase. Treating the anion-containing hydrogels with dilute HCl leads to the protonation-induced release of the bound anions. This allows the hydrogels to be recycled for reuse. The present polymer network thus provides a potentially attractive approach to removing undesired anions from aqueous environments.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Americium Separations from High-Salt Solutions Using Anion Exchange

    International Nuclear Information System (INIS)

    Barr, Mary E.; Jarvinen, Gordon D.; Stark, Peter C.; Chamberlin, Rebecca M.; Bartsch, Richard A.; Zhang, Z.Y.; Zhao, W.

    2001-01-01

    The aging of the US nuclear stockpile presents a number of challenges, including the increasing radioactivity of plutonium residues due to the ingrowth of 241 Am from the β-decay of 241 Pu. We investigated parameters that affect the sorption of Am onto anion-exchange resins from concentrated effluents derived from nitric acid processing of plutonium residues. These postevaporator wastes are nearly saturated solutions of acidic nitrate salts, and americium removal is complicated by physical factors, such as solution viscosity and particulates, as well as by the presence of large quantities of competing metals and acid. Single- and double-contact batch distribution coefficients for americium and neodymium from simple and complex surrogate solutions are presented. Varied parameters include the nitrate salt concentration and composition and the nitric acid concentration. We find that under these extremely concentrated conditions, Am(III) removal efficiencies can surpass 50% per contact. Distribution coefficients for both neodymium and americium are insensitive to solution acidity and appear to be driven primarily by low water activities of the solutions

  20. Anionic carbonato and oxalato cobalt(III) nitrogen mustard complexes.

    Science.gov (United States)

    Craig, Peter R; Brothers, Penelope J; Clark, George R; Wilson, William R; Denny, William A; Ware, David C

    2004-02-21

    Synthetic approaches to cobalt(III) complexes [Co(L)(L')2] containing the bidentate dialkylating nitrogen mustard N,N-bis(2-chloroethyl)-1,2-ethanediamine (L = dce) together with anionic ancilliary ligands (L') which are either carbonato (CO3(2-)), oxalato (ox2-), bis(2-hydroxyethyl)dithiocarbamato (bhedtc-), 2-pyridine carboxylato (pico-) or 2-pyrazine carboxylato (pyzc-) were investigated. Synthetic routes were developed using the related amines N,N-diethyl-1,2-ethanediamine (dee) and 1,2-ethanediamine (en). The complexes [Co(CO3)2(L)]- (L = dee 1, dce 2), [Co(ox)2(L)]- (L = dee 3, dce 4), [Co(bhedtc)2(dee)]+ 5, [Co(bhedtc)2(en)]+ 6, mer-[Co(pico)3], mer-[Co(pyzc)]3 7 and [Co(pico)2(dee)]+ 8 were prepared and were characterised by IR, UV-Vis, 1H and 13C[1H] NMR spectroscopy, mass spectrometry and cyclic voltammetry. [Co(bhedtc)2(en)]BPh4 6b and trans(O)-[Co(pico)2(dee)]ClO4 8 were characterised by X-ray crystallography. In vitro biological tests were carried out on complexes 1-4 in order to assess the degree to which coordination of the mustard to cobalt attenuated its cytotoxicity, and the differential toxicity in air vs. nitrogen.

  1. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    This research thesis aimed at studying the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. For this purpose, the author more particularly studied specific interactions between anionic poly-electrolytes and multivalent cations. After a recall of properties of neutral polymers and poly-electrolytes in solution, the author evokes interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. The next part presents various experimental spectroscopic and electrochemical techniques and results of the characterization of the used products. Spectroscopic techniques allow ion-polymer interactions at the atomic scale to be studied, and electrochemical techniques allow the behaviour of small ions to be studied. The author then discusses the main differences of solubility between poly-electrolytes containing sulphonate or sulphate groups and those containing carboxylate groups. A model is then developed to generalise phase diagrams of a poly-electrolyte with respect to the chemical affinity of its functional group with ions of opposite sign. The author then addresses the behaviour of a non charged polyacrylic acid in various saline solutions, and presents a phase diagram model [fr

  2. Origin of negative resistance in anion migration controlled resistive memory

    Science.gov (United States)

    Banerjee, Writam; Wu, Facai; Hu, Yuan; Wu, Quantan; Wu, Zuheng; Liu, Qi; Liu, Ming

    2018-03-01

    Resistive random access memory (RRAM) is one of the most promising emerging nonvolatile technologies for the futuristic memory devices. Resistive switching behavior often shows negative resistance (NR), either voltage controlled or current controlled. In this work, the origin of a current compliance dependent voltage controlled NR effect during the resetting of anion migration based RRAM devices is discussed. The N-type voltage controlled NR is a high field driven phenomena. The current conduction within the range of a certain negative voltage is mostly dominated by space charge limited current. But with the higher negative voltage, a field induced tunneling effect is generated in the NR region. The voltage controlled NR is strongly dependent on the compliance current. The area independent behavior indicates the filamentary switching. The peak to valley ratio (PVR) is > 5. The variation of PVR as a function of the conduction band offset is achieved. Compared to other reported works, based on the PVR, it is possible to distinguish the RRAM types. Generally, due to the higher electric field effect on the metallic bridge during RESET, the electrochemical metallization type RRAM shows much higher PVR than the valance change type RRAM.

  3. Purification of degraded TBP solvent using macroreticular anion exchange resin

    International Nuclear Information System (INIS)

    Kartha, P.K.S.; Kutty, P.V.E.; Janaradanan, C.; Ramanujam, A.; Dhumwad, R.K.

    1989-01-01

    Tri-n-butyl phosphate (TBP) diluted with a suitable diluent is commonly used for solvent extraction in Purex process for the recovery of uranium and plutonium from irradiated nuclear fuels. This solvent gets degraded due to various factors, the main degradation product being dibutyl phosphoric acid (HDBP). A solvent cleanup step is generally incorporated in the process for removing the degradation products from the used solvent. A liquid-liquid cleanup system using sodium carbonate or sodium hydroxide solution is routinely used. Considering certain advantages, like the possibility of loading the resin almost to saturation capacity and the subsequent disposal of the spent resin by incineration and the feasibility of adopting it to the process, a liquid-solid system has been tried as an alternate method, employing various available macroreticular anion exchange resins in OH - form for the sorption of HDBP from TBP. After standardizing the various conditions for the satisfactory removal of HDBP from TBP using synthetic mixtures, resins were tested with process solvent in batch contacts. The parameters studied were (1) capacity of different resins for HDBP sorption (2) influence of acidity, uranium and HDBP on the sorption behaviour of the latter (3) removal of fission products from the solvent by the resin and (4) regeneration and recycling of the resin. (author). 2 figs., 13 tabs., 17 refs

  4. Highly conductive side chain block copolymer anion exchange membranes.

    Science.gov (United States)

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  5. Cation and anion monitoring in a wastewater treatment pilot project

    Directory of Open Access Journals (Sweden)

    Magda de Almeida

    2015-01-01

    Full Text Available El propósito del tratamiento de aguas residuales es la reutilización del agua.Esta reduce el consumo de agua potable y previene la contaminación del agua de primeruso. La reutilización del agua ya se ha implementado con éxito en diferentes lugares. Lostratamientos que utilizan los humedales artifi ciales son ampliamente estudiados como unaalternativa más económica y ecológica para tratar las aguas residuales. En estos sistemas, elcontrol de especies inorgánicas también es importante. Este estudio ha monitoreado cationes (Na+, K+, Li+ y NH4+ y aniones (SO42-, NO3-, NO2-, Cl- y PO42- en un sistema de humedalesconstruido (CWs, en un sistema de captación de agua de lluvia, en el tratamiento de aguasresiduales y en agua reutilizable fi nal. El monitoreo se llevó a cabo utilizando el análisiscromatográfi co de iones. Los valores de remoción encontrados en CWs fueron: 99,9% K+,NH4+ y SO42-, 52,6% Na+, 89,8% NO3-, 98,2% NO2-, 63,6% Cl- y 96,8% PO42-. Los resultadostambién mostraron que el sistema CWs está adecuado para la eliminación de iones del aguaresidual.

  6. Anionic silicate organic frameworks constructed from hexacoordinate silicon centres

    Science.gov (United States)

    Roeser, Jérôme; Prill, Dragica; Bojdys, Michael J.; Fayon, Pierre; Trewin, Abbie; Fitch, Andrew N.; Schmidt, Martin U.; Thomas, Arne

    2017-10-01

    Crystalline frameworks composed of hexacoordinate silicon species have thus far only been observed in a few high pressure silicate phases. By implementing reversible Si-O chemistry for the crystallization of covalent organic frameworks, we demonstrate the simple one-pot synthesis of silicate organic frameworks based on octahedral dianionic SiO6 building units. Clear evidence of the hexacoordinate environment around the silicon atoms is given by 29Si nuclear magnetic resonance analysis. Characterization by high-resolution powder X-ray diffraction, density functional theory calculation and analysis of the pair-distribution function showed that those anionic frameworks—M2[Si(C16H10O4)1.5], where M = Li, Na, K and C16H10O4 is 9,10-dimethylanthracene-2,3,6,7-tetraolate—crystallize as two-dimensional hexagonal layers stabilized in a fully eclipsed stacking arrangement with pronounced disorder in the stacking direction. Permanent microporosity with high surface area (up to 1,276 m2 g-1) was evidenced by gas-sorption measurements. The negatively charged backbone balanced with extra-framework cations and the permanent microporosity are characteristics that are shared with zeolites.

  7. 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}.

  8. Purification of bacteriophage M13 by anion exchange chromatography.

    Science.gov (United States)

    Monjezi, Razieh; Tey, Beng Ti; Sieo, Chin Chin; Tan, Wen Siang

    2010-07-01

    M13 is a non-lytic filamentous bacteriophage (phage). It has been used widely in phage display technology for displaying foreign peptides, and also for studying macromolecule structures and interactions. Traditionally, this phage has been purified by cesium chloride (CsCl) density gradient ultracentrifugation which is highly laborious and time consuming. In the present study, a simple, rapid and efficient method for the purification of M13 based on anion exchange chromatography was established. A pre-packed SepFast Super Q column connected to a fast protein liquid chromatography (FPLC) system was employed to capture released phages in clarified Escherichia coli fermented broth. An average yield of 74% was obtained from a packed bed mode elution using citrate buffer (pH 4), containing 1.5 M NaCl at 1 ml/min flow rate. The purification process was shortened substantially to less than 2 h from 18 h in the conventional ultracentrifugation method. SDS-PAGE revealed that the purity of particles was comparable to that of CsCl gradient density ultracentrifugation method. Plaque forming assay showed that the purified phages were still infectious. Copyright 2010 Elsevier B.V. All rights reserved.

  9. Development of Preparation Methods for Alkaline Anion Exchange Membranes by Radiation

    International Nuclear Information System (INIS)

    Shin, Jun Hwa; Nho, Young Chang; Sohn, Joon Yong

    2010-01-01

    The objective of this project is to contribute to the environmentally friendly fuel cell system by developing a radiation grafting method for the preparation of anion exchange membranes for alkaline fuel cell and finally to the radiation technology industry. In this project, the preparation methods for the VBC-grafted fluoropolymer films using radiation have been developed and anion exchange membranes have been prepared via the reaction between the VBC-grafted fluoropolymer films and amines. The prepared anion exchange membranes were characterized and the performance of the membranes were evaluated

  10. Azid sodný a animální modely Alzheimerovy nemoci. Část I – chronická subkutánní aplikace mladým zvířatům, behaviorální testy a biochemická analýza mozku mladých zvířat

    Czech Academy of Sciences Publication Activity Database

    Krištofíková, Z.; Ort, Michael; Helešic, V.; Bureš, Jan; Řípová, D.

    2006-01-01

    Roč. 10, č. S3 (2006), s. 39-42 ISSN 1211-7579 R&D Projects: GA MŠk(CZ) 1M0517 Institutional research plan: CEZ:AV0Z50110509 Keywords : sodium azide * Alzheimer disease * animal model Subject RIV: FH - Neurology

  11. 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.

  12. 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.

  13. 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).

  14. Rhodium(II-Catalysed Intramolecular O-H Insertion of a-Diazo-g-Azido-d-Hydroxy-b-Ketoesters: Evidence for a Novel Sigmatropic Rearrangement of an Allylic Azide Intermediate

    Directory of Open Access Journals (Sweden)

    Padwa Albert

    1999-01-01

    Full Text Available The Rh2(OAc4 catalyzed intramolecular O-H insertion reaction of delta-hydroxy-alpha-diazoesters affords 3(2H-furanone-2-carboxylates in good yield but with moderate selectivity (d.e. ca 60%. The initially formed 2,5-substituted cis-furanones were found to epimerize to the corresponding 2,5-trans isomers when subjected to silica gel chromatography. The Rh2(OAc4 catalyzed decomposition of gamma-azido-delta-hydroxy-alpha-diazoesters also furnished 3(2H-furanone-2-carboxylates. These compounds are derived by a sequential O-H insertion reaction followed by a concerted [3,3]-sigmatropic shift of the allylic azide intermediate.

  15. Novel 99mTc(III)-azide complexes [99mTc(N3)(CDO)(CDOH)2B-R] (CDOH2 = cyclohexanedione dioxime) as potential radiotracers for heart imaging

    International Nuclear Information System (INIS)

    Liu, Min; Zheng, Yumin; Avcibasi, Ugur; Liu, Shuang

    2016-01-01

    Introduction: In this study, novel 99m Tc(III)-azide complexes [ 99m Tc(N 3 )(CDO)(CDOH) 2 B-R] ( 99m Tc-ISboroxime-N 3 : R = IS; 99m Tc-MPboroxime-N 3 : R = MP; 99m Tc-PAboroxime-N 3 : R = PA; 99m Tc-PYboroxime-N 3 : R = PY; and 99m Tc-Uboroxime-N 3 : R = 5U) were evaluated as heart imaging agents. Methods: Complexes [ 99m Tc(N 3 )(CDO)(CDOH) 2 B-R] (R = IS, MP, PA, PY and 5U) were prepared by ligand exchange between NaN 3 and [ 99m TcCl(CDO)(CDOH) 2 B-R]. Biodistribution and imaging studies were carried out in Sprague–Dawley rats. Image quantification was performed to compare their initial heart uptake and myocardial retention. Results: 99m Tc-ISboroxime-N 3 , 99m Tc-PYboroxime-N 3 and 99m Tc-Uboroxime-N 3 were prepared with high RCP (93–98%) while the RCP of 99m Tc-MPboroxime-N 3 and 99m Tc-PAboroxime-N 3 was 80–85%. The myocardial retention curves of 99m Tc-ISboroxime-N 3 , 99m Tc-PYboroxime-N 3 and 99m Tc-Uboroxime-N 3 were best fitted to the bi-exponential decay function. The half-time of the fast component was 1.6 ± 0.4 min for 99m Tc-ISboroxime-N 3 , 0.7 ± 0.1 min for 99m Tc-PYboroxime-N 3 and 0.9 ± 0.4 min for 99m Tc-Uboroxime-N 3 . The 2-min heart uptake from biodistribution studies followed the ranking order of 99m Tc-ISboroxime-N 3 (3.60 ± 0.68%ID/g) > 99m Tc-PYboroxime-N 3 (2.35 ± 0.37%ID/g) ≫ 99m Tc-Uboroxime-N 3 (1.29 ± 0.06%ID/g). 99m Tc-ISboroxime-N 3 had the highest 2-min heart uptake among 99m Tc radiotracers revaluated in SD rats. High quality SPECT images were obtained with the right and left ventricular walls being clearly delineated. The best image acquisition window was 0–5 min for 99m Tc-ISboroxime-N 3 . Conclusion: Both azide coligand and boronate caps had significant impact on the heart uptake and myocardial retention of complexes [ 99m Tc(N 3 )(CDO)(CDOH) 2 B-R]. Among the radiotracers evaluated in SD rats, 99m Tc-ISboroxime-N 3 has the highest initial heart uptake with the heart retention comparable to that of 99m Tc

  16. Preparation of anion exchange membrane using polyvinyl chloride (PVC) for alkaline water electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Gab-Jin; Bong, Soo-Yeon; Ryu, Cheol-Hwi [Hoseo University, Asan (Korea, Republic of); Lim, Soo-Gon [Energy and Machinery Korea Co., Ltd., Changwon (Korea, Republic of); Choi, Ho-Sang [Kyungil University, Gyeongsan (Korea, Republic of)

    2015-09-15

    An anion exchange membrane was prepared by the chloromethylation and the amination of polyvinyl chloride (PVC), as the base polymer. The membrane properties of the prepared anion exchange membrane, including ionic conductivity, ion exchange capacity, and water content were measured. The ionic conductivity of the prepared anion exchange membrane was in the range of 0.098x10{sup -2} -7.0x10{sup -2}S cm{sup -1}. The ranges of ion exchange capacity and water content were 1.9-3.7meq./g-dry-membrane and 35.1-63.1%, respectively. The chemical stability of the prepared anion exchange membrane was tested by soaking in 30 wt% KOH solution to determine its availability as a separator in the alkaline water electrolysis. The ionic conductivity during the chemical stability test largely did not change.

  17. 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

  18. 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.

  19. Feasibility Study for the Reduction of Perchlorate, Iodide, and Other Aqueous Anions

    National Research Council Canada - National Science Library

    Clewell, Rebecca A; Tsui, David T; Mattie, David R

    1999-01-01

    Cyclic Voltammetry (CV) was used as a technique to determine the feasibility of the use of a coulometric detector in the determination of perchlorate, iodide, and various other anions commonly found in drinking water...

  20. 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.

  1. Structure and dynamics of solvated hydrogenoxalate and oxalate anions: theoretical study

    Czech Academy of Sciences Publication Activity Database

    Kroutil, O.; Minofar, Babak; Kabeláč, M.

    2016-01-01

    Roč. 22, č. 9 (2016), s. 210 ISSN 1610-2940 Institutional support: RVO:61388971 Keywords : Ab initio molecular dynamics * oxalic acid anions * Potential energy surface Subject RIV: EE - Microbiology, Virology Impact factor: 1.425, year: 2016

  2. Ammonia-hydrogen bromide and ammonia-hydrogen iodide complexes: anion photoelectron and ab initio studies.

    Science.gov (United States)

    Eustis, S N; Whiteside, A; Wang, D; Gutowski, M; Bowen, K H

    2010-01-28

    The ammonia-hydrogen bromide and ammonia-hydrogen iodide, anionic heterodimers were studied by anion photoelectron spectroscopy. In complementary studies, these anions and their neutral counterparts were also investigated via ab initio theory at the coupled cluster level. In both systems, neutral NH(3)...HX dimers were predicted to be linear, hydrogen-bonded complexes, whereas their anionic dimers were found to be proton-transferred species of the form, (NH(4)(+)X(-))(-). Both experimentally measured and theoretically predicted vertical detachment energies (VDE) are in excellent agreement for both systems, with values for (NH(4)(+)Br(-))(-) being 0.65 and 0.67 eV, respectively, and values for (NH(4)(+)I(-))(-) being 0.77 and 0.81 eV, respectively. These systems are discussed in terms of our previous study of (NH(4)(+)Cl(-))(-).

  3. 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.

  4. The complex compounds of manganese (II) with poly dental ligands and polyhedron borane anions

    International Nuclear Information System (INIS)

    Buranova, S.A.

    1996-01-01

    The purpose of the present work is synthesis of complex compounds of manganese with organic ligands. Their studying by spectroscopic methods purposely to determinate the influence of borane anions on composition and structure of coordinating sphere of manganese

  5. 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.

  6. Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

    KAUST Repository

    Zhang, Hefeng; Qu, Chengke; He, Junpo

    2015-01-01

    We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b

  7. QUANTITATIVE ANALYSIS OF RELATIONSHIP STRUCTURE AND ANIONIC SURFACTANT MICELLE CONCENTRATION CRITIC WITH SEMIEMPIRIS AM1

    Directory of Open Access Journals (Sweden)

    Eva Vaulina Yulistia Delsy

    2017-05-01

    Full Text Available This research determines the mathematical equation which calculate the Concentration Micelle Critic theoretical anionic surfactant. The research was conducted the depiction of each surfactant anionic three-dimensional compound models, followed by optimizing the model structure anionic surfactant by using AM1 calculation method. Furthermore the calculation of descriptors (QSPR method, then it was analyzed statistically using Multiple Linear Regression (MLR. The results of statistical calculations showed that to calculate the theoretical CMC anionic surfactant can use the QSPR equation: log CMC = 4.157+0.118qC1+7.698qC2+0.425α–0.010µ-0.129RD–0.138 log P+0.021BM–0.034Avdw, n = 100 ; r = 0.927 ; r2 = 0.860 ; SE = 0.352 ; F= 30.888 ; PRESS = 23.506

  8. L-shaped benzimidazole fluorophores: synthesis, characterization and optical response to bases, acids and anions.

    Science.gov (United States)

    Lirag, Rio Carlo; Le, Ha T M; Miljanić, Ognjen Š

    2013-05-14

    Nine L-shaped benzimidazole fluorophores have been synthesized, computationally evaluated and spectroscopically characterized. These "half-cruciform" fluorophores respond to bases, acids and anions through changes in fluorescence that vary from moderate to dramatic.

  9. Organic anion transporting polypeptide 1B transporters modulate hydroxyurea pharmacokinetics.

    Science.gov (United States)

    Walker, Aisha L; Lancaster, Cynthia S; Finkelstein, David; Ware, Russell E; Sparreboom, Alex

    2013-12-15

    Hydroxyurea is currently the only FDA-approved drug that ameliorates the pathophysiology of sickle cell anemia. Unfortunately, substantial interpatient variability in the pharmacokinetics (PK) of hydroxyurea may result in variation of the drug's efficacy. However, little is known about mechanisms that modulate hydroxyurea PK. Recent in vitro studies identifying hydroxyurea as a substrate for organic anion transporting polypeptide (OATP1B) transporters prompted the current investigation assessing the role of OATP1B transporters in modulating hydroxyurea PK. Using wild-type and Oatp1b knockout (Oatp1b(-/-)) mice, hydroxyurea PK was analyzed in vivo by measuring [(14)C]hydroxyurea distribution in plasma, kidney, liver, urine, or the exhaled (14)CO2 metabolite. Plasma levels were significantly reduced by 20% in Oatp1b(-/-) mice compared with wild-type (area under the curve of 38.64 or 48.45 μg·h(-1)·ml(-1), respectively) after oral administration, whereas no difference was observed between groups following intravenous administration. Accumulation in the kidney was significantly decreased by twofold in Oatp1b(-/-) mice (356.9 vs. 748.1 pmol/g), which correlated with a significant decrease in urinary excretion. Hydroxyurea accumulation in the liver was also decreased (136.6 vs. 107.3 pmol/g in wild-type or Oatp1b(-/-) mice, respectively) correlating with a decrease in exhaled (14)CO2. These findings illustrate that deficiency of Oatp1b transporters alters the absorption, distribution, and elimination of hydroxyurea thus providing the first in vivo evidence that cell membrane transporters may play a significant role in modulating hydroxyurea PK. Future studies to investigate other transporters and their role in hydroxyurea disposition are warranted for understanding the sources of variation in hydroxyurea's PK.

  10. Ionic Resistance and Permselectivity Tradeoffs in Anion Exchange Membranes

    KAUST Repository

    Geise, Geoffrey M.

    2013-10-23

    Salinity gradient energy technologies, such as reverse electrodialysis (RED) and capacitive mixing based on Donnan potential (Capmix CDP), could help address the global need for noncarbon-based energy. Anion exchange membranes (AEMs) are a key component in these systems, and improved AEMs are needed in order to optimize and extend salinity gradient energy technologies. We measured ionic resistance and permselectivity properties of quaternary ammonium-functionalized AEMs based on poly(sulfone) and poly(phenylene oxide) polymer backbones and developed structure-property relationships between the transport properties and the water content and fixed charge concentration of the membranes. Ion transport and ion exclusion properties depend on the volume fraction of water in the polymer membrane, and the chemical nature of the polymer itself can influence fine-tuning of the transport properties to obtain membranes with other useful properties, such as chemical and dimensional stability. The ionic resistance of the AEMs considered in this study decreased by more than 3 orders of magnitude (i.e., from 3900 to 1.6 Ω m) and the permselectivity decreased by 6% (i.e., from 0.91 to 0.85) as the volume fraction of water in the polymer was varied by a factor of 3.8 (i.e., from 0.1 to 0.38). Water content was used to rationalize a tradeoff relationship between the permselectivity and ionic resistance of these AEMs whereby polymers with higher water content tend to have lower ionic resistance and lower permselectivity. The correlation of ion transport properties with water volume fraction and fixed charge concentration is discussed with emphasis on the importance of considering water volume fraction when interpreting ion transport data. © 2013 American Chemical Society.

  11. Monohydrocalcite: a promising remediation material for hazardous anions

    International Nuclear Information System (INIS)

    Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

    2011-01-01

    The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO 3 ·H 2 O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO 4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO 4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO 4 than calcite and aragonite. The modes of PO 4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple

  12. Monohydrocalcite: a promising remediation material for hazardous anions

    Science.gov (United States)

    Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

    2011-12-01

    The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption

  13. Monohydrocalcite: a promising remediation material for hazardous anions

    Directory of Open Access Journals (Sweden)

    Keisuke Fukushi, Takashi Munemoto, Minoru Sakai and Shintaro Yagi

    2011-01-01

    Full Text Available The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3centerdotH2O, as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly

  14. A C{sub 2}-symmetric ratiometric fluorescence and colorimetric anion sensor based on pyrrole derivative

    Energy Technology Data Exchange (ETDEWEB)

    Liu Ge [Department of Chemistry, Chifeng University, Chifeng 024000 (China); Shao Jie, E-mail: njshao@live.c [Department of Chemistry and Materials Science, Nanjing Forestry University, Nanjing 210037 (China)

    2011-07-15

    A C{sub 2}-symmetric fluorescence and colorimetric anion sensor (1) based on pyrrole derivative was designed and synthesized according to binding site-signaling subunit approach. The compound 1 was easily prepared by reaction of pyrrole-2,5-dicarboxaldehyde with 4-nitrophenylhydrazine in ethanol (yield=78%). In DMSO, the sensor 1 exhibited a visible color change from red to brown upon exposure to anions such as AcO{sup -} and F{sup -}; however, no obvious color changes were observed when the other tested anions (e. g. H{sub 2}PO{sub 4}{sup -}, Cl{sup -}, Br{sup -} and I{sup -}) were added. There was a significant redshift ({Delta}{lambda}{sub max}=160 nm) in UV-vis spectrum during UV-vis spectral titrations. In particular, the sensor 1 showed ratiometric fluorescence responses to anions. - Highlights: {yields} C{sub 2}-symmetric fluorescence and colorimetric anion sensor based on pyrrole derivative was designed and synthesized according to binding site-signaling subunit approach. {yields} The sensor was easily prepared by reaction of pyrrole-2,5-dicarboxaldehyde with 4-nitrophenylhydrazine in ethanol (yield=78%). {yields} In DMSO, the sensor exhibited a visible color change from red to brown upon exposure to anions such as AcO{sup -} and F{sup -}, however, no obvious color changes were observed when the other anions tested (e. g. H{sub 2}PO{sub 4}{sup -}, Cl{sup -}, Br{sup -} and I{sup -}) were added. {yields} The sensor showed ratiometric fluorescence responses to anions.

  15. 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

  16. Removal of plutonium from nitric acid-oxalic acid solutions using anion exchange method

    International Nuclear Information System (INIS)

    Kasar, U.M.; Pawar, S.M.; Joshi, A.R.

    1999-01-01

    An anion exchange method using Amberlyst A-26 (MP) resin was developed for removal of Pu from nitric acid-oxalic acid solutions without destroying oxalate. The method consists of sorption of Pu(IV) on Amberlyst A-26, a macroporous anion exchange resin, from nitric acid-oxalic acid medium in the presence of Al(NO 3 ) 3 . Pu(IV) breakthrough capacity of Amberlyst A-26 using synthetic feed solution was determined. (author)

  17. 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)

  18. 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...

  19. 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

  20. Vibrational Fano resonances in the photodetachment of dipole-bound anions

    International Nuclear Information System (INIS)

    Edwards, Stephen T; Tully, John C; Johnson, Mark A

    2012-01-01

    A simple model for the photodetachment of dipole-bound anions is proposed where non-adiabatic coupling of vibrational states leads to a Fano resonance in the spectrum. It is found that the shape of the photodetachment spectrum depends significantly on the parameter representing molecular polarizability. The model is also applied to a Fano profile observed in the photodetachment of small water cluster anions.