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Sample records for neutral phosphonate ligand

  1. New structural forms in molecular metal phosphonates: novel tri- and hexanuclear zinc(II) cages containing phosphonate and pyrazole ligands.

    Science.gov (United States)

    Chandrasekhar, Vadapalli; Kingsley, Savariraj; Rhatigan, Brian; Lam, Matthew K; Rheingold, Arnold L

    2002-03-11

    The reaction of ZnCl(2) with tert-butylphosphonic acid and 3,5-dimethylpyrazole in the presence of triethylamine as a hydrogen chloride scavenger affords a trinuclear molecular zinc phosphonate [Zn(3)Cl(2)(3,5-Me(2)Pz)(4)(t-BuPO(3))(2)]. The structure of this compound contains a planar trizinc assembly containing two bicapping mu(3) [t-BuPO(3)](2-) ligands and terminal pyrazole and chloride ligands. In contrast an analogous reaction of ZnCl(2) with phenylphosphonic acid and 3,5-dimethylpyrazole affords a hexanuclear zinc phosphonate [Zn(6)Cl(4)(3,5-Me(2)PzH)(8)(PhPO(3))(4)]. The six zinc centers are arranged in a chairlike conformation. The four phosphonates in this complex also act as bridging tripodal mu(3) [RPO(3)](2-) ligands.

  2. Characterizing mixed phosphonic acid ligand capping on CdSe/ZnS quantum dots using ligand exchange and NMR spectroscopy.

    Science.gov (United States)

    Davidowski, Stephen K; Lisowski, Carmen E; Yarger, Jeffery L

    2016-03-01

    The ligand capping of phosphonic acid functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of solution and solid-state (31) P nuclear magnetic resonance (NMR) spectroscopy. Two phosphonic acid ligands were used in the synthesis of the QDs, tetradecylphosphonic acid and ethylphosphonic acid. Both alkyl phosphonic acids showed broad liquid and solid-state (31) P NMR resonances for the bound ligands, indicative of heterogeneous binding to the QD surface. In order to quantify the two ligand populations on the surface, ligand exchange facilitated by phenylphosphonic acid resulted in the displacement of the ethylphosphonic acid and tetradecylphosphonic acid and allowed for quantification of the free ligands using (31) P liquid-state NMR. After washing away the free ligand, two broad resonances were observed in the liquids' (31) P NMR corresponding to the alkyl and aromatic phosphonic acids. The washed samples were analyzed via solid-state (31) P NMR, which confirmed the ligand populations on the surface following the ligand exchange process. Copyright © 2015 John Wiley & Sons, Ltd.

  3. Surface engineering of SPIONs: role of phosphonate ligand multivalency in tailoring their efficacy

    Science.gov (United States)

    Lam, Tina; Avti, Pramod K.; Pouliot, Philippe; Tardif, Jean-Claude; Rhéaume, Éric; Lesage, Frederic; Kakkar, Ashok

    2016-10-01

    We report the design of scaffolds containing mono-, bis-, and tris-phosphonate coordinating groups, and a polyethylene glycol chain, for stabilizing superparamagnetic iron oxide nanoparticles (SPIONs), using simple and versatile chemistry. We demonstrate that the number of anchoring phosphonate sites on the ligand influence the colloidal stability, magnetic and biological properties of SPIONs, and the latter do not solely depend on attaching moieties that can enhance their aqueous dispersion. These parameters can be tailored by the number of conjugation sites on the ligand, as evidenced from dynamic light scattering at various salt concentrations, magnetic relaxivities and cell viability studies.

  4. Quantitative Determination and Comparison of the Surface Binding of Phosphonic Acid, Carboxylic Acid, and Catechol Ligands on TiO2 Nanoparticles.

    Science.gov (United States)

    Zeininger, Lukas; Portilla, Luis; Halik, Marcus; Hirsch, Andreas

    2016-09-12

    The adsorption, desorption, co-adsorption, and exchange behavior of phosphonic acid, carboxylic acid, and catechol derivatives on the surface of titanium oxide (anatase) nanoparticles are investigated. Thermogravimetric analysis provides a facile and fast-track quantitative determination of the wet-chemical monolayer adsorption constants and grafting densities of ten adsorbates, all under neutral pH conditions. This characterization protocol allows straightforward quantification of the relevant thermodynamic data of ligand adsorption and a comparison of ligand adsorption strengths. The reported procedure is proposed as a universal tool and it should be applicable to many other colloidal metal oxide materials. Moreover, the determined values for the adsorption constants and the monolayer grafting densities provide a toolbox for the assessment of the adsorbates' behavior in desorption, exchange, and co-adsorption equilibria. This versatile evaluation procedure will help to identify optimal monolayer-surface combinations and to evaluate critical parameters, such as monolayer robustness, ligand exchange rates, or targeted mixed assembly of functionalities.

  5. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  6. Synthesis and Characterisation of a Novel Phosphonate Ligand and Its Palladium(II Coordination Compound

    Directory of Open Access Journals (Sweden)

    Olesea Cuzan

    2017-06-01

    Full Text Available The novel N-(methylene-2-pyridine-N,N-bis(diethoxyphosphorylmethylamine ligand (L was obtained through a double Kabachnik-Fields reaction, starting from 2-aminomethyl pyridine (2-picolylamine. Based on the L ligand, a new palladium(II coordination compound [Pd(L2Cl2] has been synthetized and comprehensively characterized by spectroscopic methods (1H NMR, UV-Vis, ESI mass spectrometry and X-ray crystallography.

  7. Assembly of tetra, di and mononuclear molecular cadmium phosphonates using 2,4,6-triisopropylphenylphosponic acid and ancillary ligands.

    Science.gov (United States)

    Chandrasekhar, Vadapalli; Sasikumar, Palani; Boomishankar, Ramamoorthy

    2008-10-14

    The reaction of ArPO(3)H(2) (Ar = 2,4,6-iPr(3)-C(6)H(2)) with Cd(CH(3)COO)(2).2H(2)O using various co-ligands such as methanol, dimethylformamide (DMF) and 3,5-dimethylpyrazole (DMPZH) resulted in the formation of tetranuclear assemblies [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(CH(3)OH)(4)].3(CH(3)OH) (1), [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(DMF)(4)].3(DMF) (2) and [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(DMF)(2)(DMPZH)(2)].2(DMF).2(H(2)O) (3). In all of these compounds the tetranuclear cadmium array, containing two five-coordinate and two six-coordinate cadmium atoms, is held together by two mu(4) capping [ArPO(3)](2-) and four anisobidentate mu(2) [ArPO(2)(OH)](-) ligands. Each cadmium atom is bound to an additional ancillary ligand. The reaction of ArPO(3)H(2) with Cd(CH(3)COO)(2).2H(2)O in the presence of the chelating ligand 2,2'-bipyridine (bipy) leads to the exclusive formation of the dinuclear assembly [Cd(2)(ArPO(3)H)(4)(bipy)(2)].(CH(3)OH)(H(2)O) (4). The latter contains an eight-membered Cd(2)P(2)O(4) inorganic ring formed as a result of the bridging coordination action of two anisobidentate mu(2) [ArPO(2)(OH)](-) ligands. Each cadmium atom is bound by one chelating bipy and one monodentate [ArPO(2)(OH)](-) ligands. Use of four equivalents of 3,5-dimethylpyrazole leads to the formation of the mononuclear derivative [Cd(ArPO(3)H)(2)(DMPZH)(4)] (5). The molecular structure of the latter comprises of a central cadmium atom surrounded by six monodentate ligands. Four of these are neutral pyrazole ligands that occupy the equatorial plane; the remaining two are anionic phosphinate ligands which are present trans to each other. The thermal analysis of 1 and 4 reveals that the char residue obtained at 600 degrees C consists predominantly of Cd(2)P(2)O(7).

  8. Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

    Science.gov (United States)

    David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

    2015-12-21

    Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very

  9. A modular approach to neutral P,N-ligands: synthesis and coordination chemistry

    Science.gov (United States)

    Blasius, Clemens K; Intorp, Sebastian N; Wadepohl, Hubert

    2016-01-01

    Summary We report the modular synthesis of three different types of neutral κ2-P,N-ligands comprising an imine and a phosphine binding site. These ligands were reacted with rhodium, iridium and palladium metal precursors and the structures of the resulting complexes were elucidated by means of X-ray crystallography. We observed that subtle changes of the ligand backbone have a significant influence on the binding geometry und coordination properties of these bidentate P,N-donors. PMID:27340475

  10. Tungstate as a synergist to phosphonate-based formulation for corrosion control of carbon steel in nearly neutral aqueous environment

    Indian Academy of Sciences (India)

    B V Appa Rao; M Venkateswara Rao; S Srinivasa Rao; B Sreedhar

    2010-07-01

    Synergistic inhibition of corrosion of carbon steel in low chloride aqueous medium using tungstate as a synergist in combination with ,-(phosphonomethyl) glycine (BPMG) and zinc ions is presented. The synergistic action of tungstate has been established through the present studies. The new ternary inhibitor formulation is effective in neutral and slightly acidic as well as slightly alkaline media. Potentiodynamic polarisation studies inferred that the formulation functions as a mixed inhibitor. Impedance studies of the metal/solution interface revealed that the surface film is highly protective. Characterisation by X-ray photoelectron spectroscopy (XPS) of the surface film formed in presence of the inhibitor revealed the presence of iron, phosphorus, nitrogen, oxygen, carbon, zinc and tungsten in the surface film. The chemical shifts in the binding energies of these elements inferred that the surface film is composed of iron oxides/hydroxides, zinc hydroxide, heteropolynuclear complex [Fe(III), Zn(II)-BPMG] and WO3. Reflection absorption FTIR spectroscopic studies also supported the presence of these compounds in the surface film. Morphological features of the metal surface studied in the absence and presence of the inhibitor by scanning electron microscopy (SEM) are also presented. Based on all these results, a plausible mechanism of corrosion inhibition is proposed.

  11. Neutral tridentate PNP ligands and their hybrid analogues: versatile non-innocent scaffolds for homogeneous catalysis.

    Science.gov (United States)

    van der Vlugt, Jarl Ivar; Reek, Joost N H

    2009-01-01

    Ligands in coordination chemistry and homogeneous catalysis are traditionally "static" spectators that do not actively participate in the catalytic cycle. However, such classic systems do not provide additional "handles" that could facilitate or trigger alternative productive reaction pathways. Recent advances in the use of novel nitrogen-centered pincer systems have unveiled interesting opportunities for cooperative catalysis. The chemistry of pyridine-derived, neutral ligands is discussed, with a specific focus on their non-innocent behavior and potential as facilitators for metal-mediated organic transformations. This overview should provide inspiration and an incentive to incorporate non-innocent ligands and their metal complexes within old and new homogeneously catalyzed reactions.

  12. DNA-interaction and in vitro antimicrobial studies of some mixed-ligand complexes of cobalt(II) with fluoroquinolone antibacterial agent ciprofloxacin and some neutral bidentate ligands.

    Science.gov (United States)

    Patel, M N; Chhasatia, M R; Gandhi, D S

    2009-05-15

    Six new mixed-ligand complexes of Co(II) with ciprofloxacin (Cip) and neutral bidentate ligands have been synthesized and characterized. Binding and cleavage of DNA with the complex were investigated using spectroscopic method, viscosity measurements and gel electrophoresis techniques. Antibacterial activity has been assayed against two Gram((-ve)) and three Gram((+ve)) microorganisms using the doubling dilution technique.

  13. A novel terbium complex using oxadiazole derivative as a neutral ligand: Synthesis and properties

    Institute of Scientific and Technical Information of China (English)

    Yu Liu; Kong Qiang Xing; Ji Yong Deng; Mei Xiang Zhu; Xia Yu Wang; Wei Guo Zhu

    2007-01-01

    A novel terbium complex using 1,3,4-oxadiazole derivative as a neutral ligand was synthesized and characterized. Its thermal stability and photoluminescent properties were studied. The strong emission peaked at 546 nm with a full width at half maximum of 5 nm was observed in the pure terbium complex film under excitation of 328 nm light, which is attributed to the characteristic emission of terbium ion. The good thermal stability and intense sharp emission of this terbium complex display its potential application in electroluminescence devices.

  14. Transition metal complexes supported by a neutral tetraamine ligand containing N,N-dimethylaniline units.

    Science.gov (United States)

    Chu, Lei; Hardcastle, Kenneth I; MacBeth, Cora E

    2010-08-16

    First-row transition metal-halide complexes of tris(2-dimethylaminophenyl)amine, L(Me), have been synthesized and characterized. X-ray crystallographic studies on [Co(L(Me))Br]BPh(4), [Ni(L(Me))Cl]BPh(4), [Fe(L(Me))Cl]BPh(4), and [Cu(L(Me))Cl]BF(4) have been performed, and in all cases the ligand produces five-coordinate complexes with distorted trigonal bipyramidal coordination geometries. Where possible, comparisons have been made to the structures of related neutral tripodal ligands. Spectroscopic and magnetic studies of these complexes are also described. The Cu(I)-carbonyl complexes [Cu(L(Me))(CO)]PF(6) and [Cu(Me(6)tren)(CO)]PF(6) (Me(6)tren = tris(N,N-dimethylaminoethyl)amine) have also been prepared. Infrared spectroscopic investigations of these carbonyl complexes confirm that L(Me) is a less electron donating ligand than Me(6)tren and indicate that L(Me) can impart a different coordination number in the solid-state.

  15. Luminescence properties of compounds of europium(III) with quinaldic acid and phosphor-containing neutral ligands

    Science.gov (United States)

    Kalinovskaya, I. V.

    2016-06-01

    Luminescent complex mixed-ligand compounds of europium(III) with quinaldic acid and phosphor- containing neutral ligands have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the obtained complex mixed-ligand compounds of europium( III) have been studied. It is shown that, during thermolysis, a water molecule and neutral ligand are detached in two stages with endothermic effects. It is established that quinaldinate ion is coordinated to europium(III) ion in a bidentate fashion. The Stark structure of the 5 D 0-7 F j ( j = 0, 1, 2) transitions in low-temperature luminescence spectra of complex compounds of europium(III) has been analyzed.

  16. Synthesis, Characterization of Neutral Nickel Complexes Bearing N-Fluorophenylsalicylaldimine Chelate Ligands and Their Catalytic Activity to Ethylene Oligomerization

    Institute of Scientific and Technical Information of China (English)

    赵蔚; 黄吉玲; 朱仕正

    2005-01-01

    A series of neutral nickel complexes featuring N-fluorophenylsalicylaldimine chelate ligands was synthesized,and the molecular structure of complex 4 was further confirmed by X-ray crystallographic analysis. The neutral nickel complexes showed high activity up to 4.22×105 g oligomers/(mol Nioh) and high selectivity to C6 olefins in catalyzing ethylene oligomerization using methylaluminoxane (MAO) as cocatalyst.

  17. Synthesis of a New Type of Amphilic and Water - soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N(CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in goodyield; the palladium (Ⅱ) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratiowere also prepared and characterized.

  18. Metal ions directed assembly of two coordination polymers based on an organic phosphonate anion and a multidentate N-donor ligand

    Science.gov (United States)

    Kan, Wei-Qiu; Xu, Ji-Ming; Wen, Shi-Zheng; Yang, Lin

    2017-01-01

    Two new coordination polymers [Cd(4,4‧-tmbpt)(HL)(H2O)] (1) and [Cu(4,4‧-tmbpt)(HL)]·H2O (2) (H3L = 2‧-carboxybiphenyl-4-ylmethylphosphonic and 4,4‧-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole) have been synthesized hydrothermally. The two compounds have the same metal to ligand ratio, but different metal ions. As a result, the two compounds display different 2D layer structures, which is mainly caused by the different coordination numbers of the different metal ions. The effects of the metal ions on the structures, the optical band gaps and photoluminescent and photocatalytic properties of the compounds have been studied.

  19. Synthesis, Characterization and Ethylene Oligomerization Behavior of Neutral Nickel Complexes Bearing N-Fluorinated Phenyl Salicylaldiminato Chelate Ligands

    Institute of Scientific and Technical Information of China (English)

    宋力平; 宋绍迪; 黄吉玲

    2012-01-01

    A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic analy- sis. The neutral nickel complexes showed high activity up to 9.96× 10^5 g oligomers/(mol Nioh) and high selectivity of C6 in catalyzing ethylene oligomerization using methylaluminoxane (MAO) as cocatalyst. It was observed that the strong electron-withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalytic activity for oligomerization of ethylene. In addition, the influence of reaction parameters such as A1/Ni molar ratio, reaction temperature, a variety of cocatalyst and ethylene pressure on catalytic activity was investigated.

  20. Syntheses and structural characterization of mercury (II) coordination polymers with neutral bidentate flexible pyrazole-based ligands

    Science.gov (United States)

    Lalegani, Arash; Khaledi Sardashti, Mohammad; Salavati, Hossein; Asadi, Amin; Gajda, Roman; Woźniak, Krzysztof

    2016-03-01

    Mercury(II) coordination compounds [Hg(μ-bbd)(μ-SCN)4]n(1) and [Hg(bpp)(SCN)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), NCS- ligand and appropriate mercury(II) salts. Compound 1 forms a polymeric network with moieties which are connected by SCN groups and the mercury ions present as HgN3S2 trigonal bipyramides. The crystal structure of 2 is build of monomers and the mercury(II) ion adopts an HgN2S2 tetrahedral geometry. In the complex 1, each bbd acts as bridging ligand connecting Hg(μ-SCN)4 ions, while in the complex 2, the bpp ligand is coordinated to an mercury(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Moreover, in the tetrahedral structure of 2, the neutral molecules form a 1D chain structure through the C-H···N hydrogen bonds, whereas in 1 no hydrogen bonds are observed. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction.

  1. Titanium-zirconium-phosphonate hybrid film on 6061 aluminum alloy

    Institute of Scientific and Technical Information of China (English)

    Shuanghong WANG; Lei WANG; Changsheng LIU

    2011-01-01

    Three titanium-zirconium-phosphonate hybrid films were formed on AA6061 aluminum alloy by immersing in fluorotitanic acid and fluorozirconic acid based solution containing different phosphonic acids for protective coatings of aluminium alloy. The corrosion resistance of three hybrid films as the substitute for chromate film were evaluated and compared. The neutral salt spray test was explored,the immersion test was conducted and electrochemical test was also executed. The hybrid films exhibited well-pleasing corrosion resistance and adhesion to epoxy resin paints. It was found out that the hybrid films could efficiently be a substitute for chromate based primer over aluminium alloy.

  2. [Amino(iminiomethyl]phosphonate

    Directory of Open Access Journals (Sweden)

    Ting-Hai Yang

    2010-09-01

    Full Text Available The title compound, CH5N2O3P, exists as a zwitterion. The N atom of the imino group is protonated and the phosphonic acid group is deprotonated. The molecular geometry about the central C atom of this zwitterionic species was found to be strictly planar with the sum of the three angles about C being precisely 360°. In the crystal, the molecules are interlinked by O—H...O and N—H...O hydrogen-bonding interactions, forming a three-dimensional supramolecular network structure.

  3. Experimental and theoretical studies on extraction of actinides and lanthanides by alicyclic H-phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Annam, Suresh; Sivaramakrishna, Akella; Vijayakrishna, Kari [VIT Univ., Tamil Nadu (India). Dept. of Chemistry; Gopakumar, Gopinadhanpillai; Rao, C.V.S. Brahmmananda; Sivaraman, N. [Indira Gandhi Centre for Atomic Research (IGCAR), Tamil Nadu (India). Chemistry Group

    2017-06-01

    Three different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid-liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in n-dodecane from nitric acid medium. The physicochemical properties of the extractants, such as density, viscosity, solubility were determined. At lower acidities, these H-phosphonates exhibit higher distribution values and the extraction following cation exchange mechanism through P-OH group of tri-coordinated phosphite form. At higher acidities (2N), the extraction is primarily via solvation mechanism through P=O group of penta-coordinated phosphonate form. Amongst the three H-phosphonates, examined dimenthyl H-phosphonate showed the best results for the actinide extraction. Density functional theory (DFT) calculations were applied to understand the electronic structure of the ligands and the metal complexes. The calculated large complexation energy of UO{sub 2}(NO{sub 3}){sub 2}.@2DMnHP is in agreement with the observed trend in experimental distribution ratio data.

  4. Extraction studies of actinides and lanthanides by bifunctional H-phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Brahmmananda Rao, C.V.S.; Jayalakshmi, S.; Subramaniam, S.; Sivaraman, N.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2015-07-01

    The extraction behavior of actinides and lanthanides was investigated by three homologues of H-phosphonates viz. diamylhydrogen phosphonate (DAHP), dihexylhydrogen phosphonate (DHeHP) and dioctylhydrogen phosphonate (DOHP). These compounds were synthesized, characterized by using elemental analysis, IR, NMR ({sup 1}H, {sup 13}C and {sup 31}P) and mass spectroscopy. The extraction behavior of these ligands was compared with a member of dialkylalkyl phosphonate viz. diamylamyl phosphonate (DAAP). The present study has been taken up to understand the influence of phosphorus bonded hydrogen and alkyl groups in H-phosphonates on the extraction behavior of actinides and lanthanides. The important physicochemical properties such as density, viscosity, phase disengagement time, dispersion number and solubility are also reported for the first time. These compounds extract actinides through the P-OH group which is present in tautomeric equilibrium with the P-H bond at lower acidities, and through the phosphoryl group at higher acidities thus exhibiting a dual behaviour. The physical properties can be modified by suitably designing the extractant based on the requirement for a given purpose. The H-phosphonates have potential applications in pre-concentration of large quantities of dilute solutions of uranium and plutonium.

  5. Lanthanide dinuclear complexes constructed from mixed oxygen-donor ligands: the effect of substituent positions of the neutral ligand on the magnetic dynamics in Dy analogues.

    Science.gov (United States)

    Zhu, Wen-Hua; Li, Shan; Gao, Chen; Xiong, Xia; Zhang, Yan; Liu, Li; Powell, Annie K; Gao, Song

    2016-03-21

    Two series of lanthanide dinuclear complexes with the general formulae, [Ln(n-PNO)(Bza)3(H2O)] {Bza = benzoic acid; n = 3, n-PNO = 3-picoline N-oxide, Dy(1) and Er(2); and n = 4, n-PNO = 4-picoline N-oxide, Nd(3), Eu(4), Gd(5), Tb(6), Dy(7), Er(8) and Y(9)} have been successfully synthesized by the hydrothermal method. Single-crystal X-ray diffraction experiments illustrate that the two series of compounds possess similar carboxylic ligand-bridged dinuclear structure and coordination geometry around the lanthanide ions despite the different methyl-substituent positions on the neutral ligand. Comparative studies of the Dy analogues in the static-field measurements reveal only a little difference with a small butterfly-shaped opening for complex 1 and a close hysteresis loop for 7 at 2.0 K. However, systematic investigations of the alternating-current (ac) measurements indicate that the different substituent positions of the picoline N-oxide ligand have a significant effect on the magnetic relaxation dynamics. A more substantial suppression of the quantum tunnelling of magnetization (QTM) effect and pronounced slow magnetic relaxation were observed in complex 7 as compared to 1 under both zero and a 1 kOe static field.

  6. The binding of phosphonic acids at aluminium oxide surfaces and correlation with passivation of aluminium flake.

    Science.gov (United States)

    Cooper, Rachel J; Camp, Philip J; Henderson, David K; Lovatt, Paul A; Nation, David A; Richards, Stuart; Tasker, Peter A

    2007-04-07

    Measurements of adsorption isotherms of a series of thirteen mono- and di-phosphonic acids have shown that these bind strongly to the surface of high surface area aluminium trihydroxide. The incorporation of such phosphonates into a suspension of aluminium flake in an aqueous medium, modelling the continuous phase of a water-based paint, greatly suppresses the evolution of hydrogen. Whilst strong binding of the phosphonate to aluminium oxides is an essential criterion for good passivation, other factors such as the hydrophobicity of the ligand are also important in suppressing hydrogen-evolution.

  7. Structure of the Escherichia coli Phosphonate Binding Protein PhnD and Rationally Optimized Phosphonate Biosensors

    Science.gov (United States)

    Alicea, Ismael; Marvin, Jonathan S.; Miklos, Aleksandr E.; Ellington, Andrew D.; Looger, Loren L.; Schreiter, Eric R.

    2012-01-01

    The phnD gene of Escherichia coli encodes the periplasmic binding protein of the phosphonate uptake and utilization pathway. We have crystallized and determined structures of E. coli PhnD (EcPhnD) in the absence of ligand and in complex with the environmentally abundant 2-aminoethylphosphonate (2AEP). Similar to other bacterial periplasmic binding proteins, 2AEP binds near the center of mass of EcPhnD in a cleft formed between two lobes. Comparison of the open, unliganded structure with the closed 2AEP-bound structure shows that the two lobes pivot around a hinge by ~70° between the two states. Extensive hydrogen bonding and electrostatic interactions stabilize 2AEP, which binds to EcPhnD with low nanomolar affinity. These structures provide insight into phosphonate uptake by bacteria and facilitated the rational design of high signal-to-noise phosphonate biosensors based both on coupled small molecule dyes and autocatalytic fluorescent proteins. PMID:22019591

  8. Comparison of competitive ligand-binding assay and bioassay formats for the measurement of neutralizing antibodies to protein therapeutics.

    Science.gov (United States)

    Finco, Deborah; Baltrukonis, Daniel; Clements-Egan, Adrienne; Delaria, Kathy; Gunn, George R; Lowe, John; Maia, Mauricio; Wong, Teresa

    2011-01-25

    Administration of biological therapeutic proteins can lead to unwanted immunogenicity in recipients of these products. The assessment and characterization of such immune reactions can be helpful to better understand their clinical relevance and how they relate to patient safety and therefore, have become an integral part of a product development program for biological therapeutics. Testing for anti-drug antibodies (ADA) to biological/biotechnology-derived therapeutic proteins generally follows a tiered approach. Samples are initially screened for binding antibodies; presumptive positives are then confirmed in a confirmatory assay; subsequently, confirmed-positive samples may be further characterized by titration and with a neutralizing antibody (NAb) assay. Regulatory guidances on immunogenicity state that assessing the neutralizing capacity of antibodies should preferably be done using functional bioassays, while recognizing that competitive ligand-binding (CLB) assays may be substituted when neutralizing bioassays are inadequate or not feasible. This manuscript describes case studies from four companies in which CLB assays and functional bioassays were compared for their ability to detect neutralizing ADA against a variety of biotechnology-derived therapeutic proteins. Our findings indicate that CLB assays are comparable to bioassays for the detection of NAbs, in some cases offering better detection sensitivity, lower variability, and less matrix interference.

  9. Synthesis and Structural Studies of Calcium and Magnesium Phosphinate and Phosphonate Compounds

    Science.gov (United States)

    Bampoh, Victoria Naa Kwale

    The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, the absence of energetically available d-orbitals to direct metal geometry, as well as the overall weakness of the metal-ligand bonds. A significant part of this project was concerned with the development of suitable reaction conditions to obtain X-ray quality crystals of the reaction products to allow for structural elucidation of the novel compounds. Various methodologies to aid in crystal growth including hydrothermal methods and gel crystallization were employed. We have used phosphinate and phosphonate ligands with different number of phosphorus oxygen atoms as well as diphosphonates with different linker lengths to determine their effects on the overall structural features. An interesting correlation is observed between the dimensionality of products and the increasing number of donor oxygen atoms in the ligands as we progress from phosphinic acid to the phosphorous acids. As an example, monophosphinate ligand only yielded one-dimensional compounds, whereas the phosphonates crystallize as one and two-dimensional compounds, and the di- and triphosphonate based compounds display two or three-dimensional geometries. This thesis provides a selection of calcium and magnesium compounds with one-dimensional geometry, as represented in a calcium phosphinate to novel

  10. Studies on the preparation and stability of samarium-153 propylene diamine tetramethylene phosphonate (PDTMP) complex as a bone seeker

    Energy Technology Data Exchange (ETDEWEB)

    Majali, M.A. E-mail: mythili@magnum.barc.ernet.in; Mathakar, A.R.; Shimpi, H.H.; Banerjee, Sharmila; Samuel, Grace

    2000-12-15

    Propylene diamine tetra methylene phosphonate (PDTMP) was synthesised by modifying a method reported for the synthesis of EDTMP. Complexation of the synthesised phosphonate ligand with {sup 153}Sm was carried out by varying the experimental parameters and the complex was radiochemically characterized. Biodistribution studies showed that the uptake by bone in rats was 2% per g of bone, which was retained up to 48 h. The uptake by other organs was insignificant, except by the liver which showed a slightly higher absorption.

  11. Adsorption phenomena of cubane-type tetranuclear Ni(II) complexes with neutral, thioether-functionalized ligands on Au(111)

    Science.gov (United States)

    Heß, Volkmar; Matthes, Frank; Bürgler, Daniel E.; Monakhov, Kirill Yu.; Besson, Claire; Kögerler, Paul; Ghisolfi, Alessio; Braunstein, Pierre; Schneider, Claus M.

    2015-11-01

    The controlled and intact deposition of molecules with specific properties onto surfaces is an emergent field impacting a wide range of applications including catalysis, molecular electronics, and quantum information processing. One strategy is to introduce grafting groups functionalized to anchor to a specific surface. While thiols and disulfides have proven to be quite effective in combination with gold surfaces, other S-containing groups have received much less attention. Here, we investigate the surface anchoring and organizing capabilities of novel charge-neutral heterocyclic thioether groups as ligands of polynuclear nickel(II) complexes. We report on the deposition of a cubane-type {Ni4} (= [Ni(μ3-Cl)Cl(HL·S)]4) single-molecule magnet from dichloromethane solution on a Au(111) surface, investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction, both immediately after deposition and after subsequent post-annealing. The results provide strong evidence for partial decomposition of the coordination complex upon deposition on the Au(111) surface that, however, leaves the magnetic {Ni4Cl4n} (n = 1 or 2) core intact. Only post-annealing above 480 K induces further decomposition and fragmentation of the {Ni4Cl4n} core. The detailed insight into the chemisorption-induced decomposition pathway not only provides guidelines for the deposition of thioether-functionalized Ni(II) complexes on metallic surfaces but also reveals opportunities to use multidentate organic ligands decorated with thioether groups as transporters for highly unstable inorganic structures onto conducting surfaces, where they are stabilized retaining appealing electronic and magnetic properties.

  12. Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Lei, E-mail: gl_coord@163.com [School of Chemistry and Materials Science, Liaoning University of Petroleum and Chemical Engineering, Fushun 113001 (China); Wang, Ying [Center of Experiment, College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning University of Petroleum and Chemical Engineering, Fushun 113001 (China)

    2015-08-15

    A novel cobalt phosphonate, [Co(HL)(H{sub 2}O){sub 3}]{sub n} (1) (L=N(CH{sub 2}PO{sub 3}H){sub 3}{sup 3−}) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO{sub 6} octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis.

  13. Distorted cubic tetranuclear vanadium(IV) phosphonate cages: double-four-ring (D4R) containing transition metal ion phosphonate cages.

    Science.gov (United States)

    Chandrasekhar, Vadapalli; Dey, Atanu; Senapati, Tapas; Sañudo, E Carolina

    2012-01-21

    The reaction of VCl(3) with 3,5-dimethylpyrazole (3,5-Me(2)PzH) and trichloromethylphosphonic/tert-butylphosphonic acid in the presence of triethylamine as a hydrogen chloride scavenger afforded the tetranuclear V(IV) assemblies, [(VO)(4)(3,5-Me(2)PzH)(8)(CCl(3)PO(3))(4)] (1) and [(VO)(4)(3,5-Me(2)PzH)(4)(t-BuPO(3))(4)] (2). Both of these compounds possess a distorted cubic framework structures containing V(IV) ions and phosphorus atoms in the alternate corners of the cube. The edges of the cube contain oxygen atoms derived from the phosphonate ligand. The phosphonate ligand in both of these compounds is dianionic and helps to bind to three V(IV) centers. The faces of the cubic ensembles contain puckered V(2)P(2)O(4) eight-membered rings. The V(IV) center in 1 is six-coordinate in a distorted octahedral geometry while in 2 it is five-coordinate in a distorted square-pyramidal geometry. Magnetic studies carried out on 1 and 2 reveal that the V(IV) centers are anti-ferromagnetically coupled to each other, albeit weakly, through the mediation of the phosphonate ligands.

  14. Synthesis and structural characterization of dinuclear Cd2+, Hg2+ and Fe2+ complexes with neutral bi and tetradentate flexible pyrazole-based ligands

    Science.gov (United States)

    Beheshti, Azizolla; Lalegani, Arash; Behvandi, Fatemeh; Safaeiyan, Forough; Sarkarzadeh, Afsoon; Bruno, Giuseppe; Amiri Rudbari, Hadi

    2015-02-01

    Four new complexes of [Hg2Cl4(bpp)]n (1), [Hg2Cl4(tdmpp)] (2), [Cd2I4(tdmpp)] (3) and [Fe2Cl4(tdmpp)] (4) were prepared by using the neutral N-donor ligands 1,3-bis(3,5-dimethyl-1-pyrazolyl)propane (bpp) and 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane (tdmpp) with different flexibility and appropriate metal salts of Cd(II), Hg(II) and Fe(II) ions. These compounds were characterized by the infrared spectroscopy, elemental analysis and X-ray crystallography. Flexible ligands and non-covalent Csbnd H⋯Cl hydrogen bonds play a major role in the crystal packing of compounds 1, 2 and 4. In the two-dimensional non-covalent structure of 1, there are two distinctly different coordination modes for the mercury atoms. One mercury atom has pseudo-trigonal bipyramidal geometry and the other adopts a distorted tetrahedral environment. In the dinuclear structures of 2 and 4 the neutral molecules are linked together by the Csbnd H⋯Cl hydrogen bonds, forming an infinite one-dimensional zigzag chain structure. Compounds 2-4 are isostructural with each other.

  15. Structure of the Escherichia coli Phosphonate Binding Protein PhnD and Rationally Optimized Phosphonate Biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Alicea, Ismael; Marvin, Jonathan S.; Miklos, Aleksandr E.; Ellington, Andrew D.; Looger, Loren L.; Schreiter, Eric R. (Puerto Rico); (HHMI); (Texas)

    2012-09-17

    The phnD gene of Escherichia coli encodes the periplasmic binding protein of the phosphonate (Pn) uptake and utilization pathway. We have crystallized and determined structures of E. coli PhnD (EcPhnD) in the absence of ligand and in complex with the environmentally abundant 2-aminoethylphosphonate (2AEP). Similar to other bacterial periplasmic binding proteins, 2AEP binds near the center of mass of EcPhnD in a cleft formed between two lobes. Comparison of the open, unliganded structure with the closed 2AEP-bound structure shows that the two lobes pivot around a hinge by {approx}70{sup o} between the two states. Extensive hydrogen bonding and electrostatic interactions stabilize 2AEP, which binds to EcPhnD with low nanomolar affinity. These structures provide insight into Pn uptake by bacteria and facilitated the rational design of high signal-to-noise Pn biosensors based on both coupled small-molecule dyes and autocatalytic fluorescent proteins.

  16. Tropolone as anionic and neutral ligand in lead(II) and bismuth(III) complexes: Synthesis, structure, characterization and computational studies

    Science.gov (United States)

    Lyczko, Krzysztof

    2017-01-01

    Two new metal complexes, [Bi(trop)2(Htrop)(CF3SO3)] (1) and [Pb(trop)2(Htrop)] (2), have been synthesized by reaction of the respective metal triflates with an excess of tropolone (Htrop) in the concentrated methanol or dimethylsulfoxide solution. In addition, it was found that complex 1 crystallizes through the formation of unstable intermediate methanol solvated tris(tropolonato)bismuth(III) compound. The characteristic behavior of tropolone which coordinates both as the bidentate anion (trop-) and the monodentate neutral molecule (Htrop) has been revealed in 1 and 2. The crystal structures of studied compounds have been determined by single-crystal X-ray diffraction. The molecular structures of both complexes have been compared with their geometries received from DFT calculations giving a good correlation. The presented compounds show coordination number of metal ion equal to five in 2 and six in 1 and the presence of stereochemically active 6s2 lone electron pair. The complexes were characterized by FT-IR, NMR and UV-Vis techniques. IR and UV-Vis spectra of 1 and 2 were also simulated by DFT methods. TD-DFT predictions demonstrate the frontier HOMOs and LUMOs cover in the major part the tropolonate and(or) tropolone moieties which gives mainly ligand-to-ligand charge transfer (LLCT) and ligand centered (LC) character to the energy bands above 300 nm.

  17. Supramolecular sensing with phosphonate cavitands.

    Science.gov (United States)

    Pinalli, Roberta; Dalcanale, Enrico

    2013-02-19

    Molecular recognition is a recurrent theme in chemical sensing because of the importance of selectivity for sensor performances. The popularity of molecular recognition in chemical sensing has resulted from the progress made in mastering weak interactions, which has enabled the design of synthetic receptors according to the analyte to be detected. However, the availability of a large pool of modular synthetic receptors so far has not had a significant impact on sensors used in the real world. This technological gap has emerged because of the difficulties in transferring the intrinsic molecular recognition properties of a given receptor from solution to interfaces and in finding high fidelity transduction modes for the recognition event. This Account focuses on the ways to overcome these two bottlenecks, and we recount our recent efforts to produce highly selective supramolecular sensors using phosphonate cavitands as receptors. Through two examples, we present an overview of the different operating strategies that are implemented depending on whether the interface is vapor-solid or liquid-solid. First we describe the selective detection of short chain aliphatic alcohols in the vapor phase. In this example, we solved a key issue common to all sensors for organic vapors: the dissection of the specific interaction (between cavitand and the alcohol) from ubiquitous nonspecific dispersion interactions (between the analytes and interferents in the solid layer). We removed responses resulting from the nonspecific interactions of the analytes with interferents by directly connecting the recognition event at the interface to the transduction mechanism (photoinduced charge transfer). The second example addresses the specific detection of sarcosine in urine. Recent research has suggested that sarcosine can serve as reliable biomarker of the aggressive forms of prostate cancer. Tetraphosphonate cavitands can complex N-methyl ammonium salts with impressive selectivity in

  18. Reactivity studies of eta sup (6)-p-cymene ruthenium(II) carboxylato complexes towards azide some neutral ligands

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Kollipara, M.R.

    complexes with NaN sub (3) yielded azido complex [{(eta sup (6)-p-cymene)Ru(mu-N sub (3))Cl} sub (2)] whereas halide scavengers such as silver acetate, silvertrifluroacetate leads to the substitution of chlorine to give neutral complexes of formulation...

  19. Measuring Binding Affinity of Protein-Ligand Interaction Using Spectrophotometry: Binding of Neutral Red to Riboflavin-Binding Protein

    Science.gov (United States)

    Chenprakhon, Pirom; Sucharitakul, Jeerus; Panijpan, Bhinyo; Chaiyen, Pimchai

    2010-01-01

    The dissociation constant, K[subscript d], of the binding of riboflavin-binding protein (RP) with neutral red (NR) can be determined by titrating RP to a fixed concentration of NR. Upon adding RP to the NR solution, the maximum absorption peak of NR shifts to 545 nm from 450 nm for the free NR. The change of the absorption can be used to determine…

  20. Cationic and neutral copper(I) iodide cluster MOFs derived from tridentate N-donor functionalized P(V) ligands: synthesis, structure and photophysical properties

    Indian Academy of Sciences (India)

    ASHOK YADAV; MAHESH S DESHMUKH; RAMAMOORTHY BOOMISHANKAR

    2017-08-01

    Formation of cationic and neutral CuI cluster MOFs have been reported starting from tridentate phosphoramide ligands, [(NHR) ₃P = E] (L¹: R = 3-aminoquinolinyl (AQ), E = S; L²: R = 3-pyridyl (PY), E = S; L³: R = 3-aminoquinolinyl (AQ), E = O). By utilizing L¹, a cationic 2D-MOF {[(L¹) ₂ (Cu₆I₅)](OH) · 3DMF·4MeOH}n, 1 containing a rugby ball shaped discrete Cu₆I₅ cluster has been reported earlier. Formation of a new 3D-MOF {[(L²) ₂ (Cu₆I₄)](OH) ₂· 2DMF}n containing a Zintl type [(Cu₆I₄4) ² ⁺]n cluster chains is reported in this paper. A neutral cluster MOFs 3 with formula unit of {[Cu₄I₄L³ (CH₃CN)] · 2DMF · 3H₂O}n has been prepared from the ligand L³. Formation of the smaller Cu₄I₄ clusters in the MOF 3 is due to the presence of a MeCN ligation at one of the Cu(I) atoms which not only precludes the extension of the assembly in three dimension but also reduces the size of the obtained cluster. Unlike 1 which showed a ligand-assisted thermochromism, photophysical studies on the 3D-MOF 2 exhibited green phosphorescence at both 298 K and 77 K. The occurrence of the phosphorescence at 77 K in 2 is due to triplet cluster centered (³CC) excited state of the cluster as there is no ligand-centered transition observed at 298 K. The 2D-MOF 3 does not show any characteristic luminescence behavior as the presence of the acetonitrile coordination at one of the Cu(I) ion is believed to quench the emission by non-radiative pathways. Further, luminescence quenching experiments on 1 and 2 with aromatic nitro-analytes showed a very high sensing selectivity for picric acid (TNP) over other aromatic nitro-analytes.

  1. Chiral hydroxy phosphonates: synthesis, configuration and biological properties

    Energy Technology Data Exchange (ETDEWEB)

    Kolodiazhnyi, Oleg I [Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev (Ukraine)

    2006-03-31

    Published data on the synthesis, absolute configurations and biological properties of chiral hydroxy phosphonates are generalised and described systematically. Examples of asymmetric synthesis of hydroxy phosphonates by the phospho-aldol reaction, reduction of keto phosphonates, chemo-enzymatic approach, and so on are discussed. Methods for determination of the optical purity and absolute configuration of hydroxy phosphonates using modification by chiral reagents, NMR, circular dichroism, GLC and HPLC on columns with chiral sorbents are considered. The significance of hydroxy phosphonates as promising compounds for the development of new drugs and bioregulators is demonstrated.

  2. Chiral hydroxy phosphonates: synthesis, configuration and biological properties

    Science.gov (United States)

    Kolodiazhnyi, Oleg I.

    2006-03-01

    Published data on the synthesis, absolute configurations and biological properties of chiral hydroxy phosphonates are generalised and described systematically. Examples of asymmetric synthesis of hydroxy phosphonates by the phospho-aldol reaction, reduction of keto phosphonates, chemo-enzymatic approach, and so on are discussed. Methods for determination of the optical purity and absolute configuration of hydroxy phosphonates using modification by chiral reagents, NMR, circular dichroism, GLC and HPLC on columns with chiral sorbents are considered. The significance of hydroxy phosphonates as promising compounds for the development of new drugs and bioregulators is demonstrated.

  3. Synthesis and applications of gem-bis-phosphonates, powerful complexing agents of metals; Synthese et applications de composes gem-bisphosphonates, de puissants complexants de metaux

    Energy Technology Data Exchange (ETDEWEB)

    Lecercle, D

    2007-12-15

    This thesis was devoted to the development of new ways to prepare gem-bis-phosphonates compounds (BPs), and was carried out under the Program of Nuclear and Environmental Toxicology (ToxNuc-E). Two applications of these compounds have been investigated, the preparation of potent ligands of the uranyl ion for a target of decorporation, and the preparation of new anticancer compounds. The first of these applications was the consequence of work done in the laboratory, that have shown the strong uranium-binding properties of bis-phosphonic ligands. The in vivo tests performed on these compounds have shown the tendency of these ligands to cause liver accumulation of uranium, we wanted to address this problem by modifying the method of anchoring of the bis-phosphonates functions. To this end we have developed a new way to access to these compounds using a metal-carbenoid mediated poly-ols and poly-amines insertion, the metal-carbenoid species bearing the bis-phosphonate function. Regarding the preparation of BPs as anticancer agents, we have developed a new synthetic pathway using a phosphine catalyzed {alpha}-P addition of phosphorated pro-nucleophiles to alkynyl-phosphonates as a key step. This enabled us to prepare thirty compound whose activity was evaluated on two cell lines (A431 and HuH7). Five of these compounds possess an activity equivalent to that of the compound described as the most active, the Zoledronate. (author)

  4. Removal and Recovery of Phosphonate Antiscalants

    NARCIS (Netherlands)

    Boels, L.

    2012-01-01

    In reverse osmosis (RO) desalination processes, the use of phosphonates prevents scaling, thus allowing for a higher product water recovery, which increases the efficiency of the process. However, a major concern associated with their use in RO desalination is the high cost and environmental impacts

  5. Removal and Recovery of Phosphonate Antiscalants

    NARCIS (Netherlands)

    Boels, L.

    2012-01-01

    In reverse osmosis (RO) desalination processes, the use of phosphonates prevents scaling, thus allowing for a higher product water recovery, which increases the efficiency of the process. However, a major concern associated with their use in RO desalination is the high cost and environmental impacts

  6. An AlCl3 based ionic liquid with a neutral substituted pyridine ligand for electrochemical deposition of aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Youxing [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Yoshii, Kazuki [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Jiang, Xueguang [Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry; Sun, Xiao-Guang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Tsuda, Tetsuya [Osaka Univ., Suita (Japan). Department of Applied Chemistry, Graduate School of Engineering; Mehio, Nada [Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry; Dai, Sheng [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry

    2015-02-04

    We study a new ionic liquid (IL) based on a neutral ligand, 4-propylpyridine, is obtained via complexation with AlCl3. It is found that the asymmetric cleavage of AlCl3 generates AlCl2+ and AlCl4 , and the former is coordinated by 4-Pr-Py to produce the Al-containing cations ([AlCl2(4-Pr-Py)2]+). The AlCl3/4-propylpyridine IL with a molar ratio of 1.3/1 is highly fluidic with a viscosity of 42.8 mPa s and an ionic conductivity of 5.0 x 10-4 S/cm at room temperature. In contrast to conventional ILs for electroplating aluminum in which the electrochemically active species are Al-containing anions (for example Al2Cl7- ), this new IL has an Al-containing cation as the electroactive species, which is beneficial to electrodeposition of aluminum.

  7. Synthesis of polymeric phosphonates for selective delivery of radionuclides to osteosarcoma.

    Science.gov (United States)

    Popwell, Sam J; Schulz, Michael D; Wagener, Kenneth B; Batich, Christopher D; Milner, Rowan J; Lagmay, Joanne; Bolch, Wesley E

    2014-09-01

    Discussed in detail is the synthesis and primary structure characterization of two polymers aimed at advancing the treatment of pediatric osteosarcoma. These polymers are designed to systemically deliver radiometals specifically to osteosarcomas using the passive targeting mechanism of enhanced permeability and retention (the EPR effect). The approach begins with the synthesis of a polymer capable of binding radiometals, for which prior data show improved site-specific targeting of solid tumors. Building on this success, a second polymer has been designed for improving the efficacy of currently available radionuclide therapies by incorporating the FDA-approved small-molecule ligand Quadramet directly onto the polymer structure. Time-activity curves of the phosphonate-functionalized polymers show rapid clearance from the central compartment and nontargeted organs, with up to 65% of injected activity being excreted within 3 hours. Both polymer ligands demonstrate good osteosarcoma targeting capability with little to no uptake in organs associated with the dose-limiting bone marrow. Additionally, biodistribution studies in nonosseous tumor models demonstrate the tumor targeting mechanism of the polymer ligands, which appears to be influenced by the high affinity of the phosphonate functionality for the positively charged hydroxyapatite mineral found in bone tumors.

  8. Stannoxanes and phosphonates: New approaches in organometallic and transition metal assemblies

    Indian Academy of Sciences (India)

    Vadapalli Chandrasekhar; Kandasamy Gopal; Loganathan Nagarajan; Palani Sasikumar; Pakkirisamy Thilagar

    2006-11-01

    Phosphonate ligands, [RPO3]2-, are extremely versatile in the assembly of multi-tin and multi-copper architectures. We have used organostannoxane cores for supporting multi-ferrocene and multi-porphyrin peripheries. The copper-metalated multi-porphyrin compound is an excellent reagent for facile cleavage of DNA, even in the absence of a co-oxidant. Reaction of -BuPO3H2 with Cu(ClO4)2. 6H2O in the presence of 2-pyridylpyrazole (2-Pypz) leads to the synthesis of a decanuclear copper (II) assembly.

  9. Sm(eta/sup 6/-C/sub 6/Me/sub 6/)(eta/sup 2/-AlCl/sub 4/)/sub 3/: the first structure of a rare earth complex with a neutral. pi. -ligand

    Energy Technology Data Exchange (ETDEWEB)

    Cotton, F.A.; Schwotzer, W.

    1986-07-23

    The authors and others have demonstrated before that one of these intercalators, UCl/sub 4/, can undergo arylation reactions to yield eta/sup 6/-arene complexes and they have structurally characterized such compounds of U(IV) and U(III). In light of the fact that U arene complexes are the only examples of neutral ..pi..-ligands bonded to f-elements, they were wondering whether uranium constitutes a special case and whether an f-orbital contribution was instrumental in the bonding. It was therefore tempting to challenge this synthetic approach with lanthanide metals for which there is no structurally characterized complex with neutral ..pi..-ligands on record. They have chosen a known intercalator of graphite and wish to report here on the first arene complex of a rare earth element, Sm(eta/sup 6/-C/sub 6/Me/sub 6/)(AlCl/sub 4/)/sub 3/-1.5 toluene.

  10. Designer discodermolide segments via ozonolysis of vinyl phosphonates.

    Science.gov (United States)

    Mollat du Jourdin, Xavier; Noshi, Mohammad; Fuchs, P L

    2009-02-01

    To apply our collection of enantiopure 7-ring vinyl sulfones to probe the anticancer SAR of a series of computer-designed (+)-discodermolide analogs, the ozonolytic reactivity of transposed cyclic vinyl phosphonates was explored. Successful preparation of the desired aldehyde-esters and lactones from vinyl phosphonates via an oxidative cleavage-phosphite/methanol exchange sequence is described.

  11. Epoxy Phosphonate Crosslinkers for Providing Flame Resistance to Cotton Textiles

    Science.gov (United States)

    Two new monomers (2-methyl-oxiranylmethyl)-phosphonic acid dimethyl ester (3) and [2-(dimethoxy-phosphorylmethyl)-oxyranylmethyl]-phosphonic acid dimethyl ester (6) were prepared and used with dicyandiamide (7) and citric acid (8) to impart flame resistance to cotton plain weave, twill, and 80:20-co...

  12. Delayed hepatic uptake of multi-phosphonic acid poly(ethylene glycol) coated iron oxide measured by real-time Magnetic Resonance Imaging

    CERN Document Server

    Ramniceanu, G; Vezignol, C; Graillot, A; Loubat, C; Mignet, N; Berret, J -F

    2016-01-01

    We report on the synthesis, characterization, stability and pharmacokinetics of novel iron based contrast agents for magnetic resonance imaging (MRI). Statistical copolymers combining multiple phosphonic acid groups and poly(ethylene glycol) (PEG) were synthesized and used as coating agents for 10 nm iron oxide nanocrystals. In vitro, protein corona and stability assays show that phosphonic acid PEG copolymers outperform all other coating types examined, including low molecular weight anionic ligands and polymers. In vivo, the particle pharmacokinetics is investigated by monitoring the MRI signal intensity from mouse liver, spleen and arteries as a function of the time, between one minute and seven days after injection. Iron oxide particles coated with multi-phosphonic acid PEG polymers are shown to have a blood circulation lifetime of 250 minutes, i.e. 10 to 50 times greater than that of recently published PEGylated probes and benchmarks. The clearance from the liver takes in average 2 to 3 days and is indep...

  13. C-H hydroxylation of phosphonates with oxygen in [bmIm]OH To produce quaternary α-hydroxy phosphonates.

    Science.gov (United States)

    Li, Xiangguang; Jin, Cheng; Gu, Lijun

    2015-02-20

    A highly efficient and mild [bmIm]OH-catalyzed α-hydroxylation of phosphonates using O2 as the oxygen source is described. The employment of ionic liquid under mild reaction conditions makes this transformation green and practical. Especially, this reaction provided a novel and convenient methodology for the construction of quaternary α-hydroxy phosphonates.

  14. Phosphonate-anchored monolayers for antibody binding to magnetic nanoparticles.

    Science.gov (United States)

    Benbenishty-Shamir, Helly; Gilert, Roni; Gotman, Irena; Gutmanas, Elazar Y; Sukenik, Chaim N

    2011-10-04

    Targeted delivery of magnetic iron oxide nanoparticles (IONPs) to a specific tissue can be achieved by conjugation with particular biological ligands on an appropriately functionalized IONP surface. To take best advantage of the unique magnetic properties of IONPs and to maximize their blood half-life, thin, strongly bonded, functionalized coatings are required. The work reported herein demonstrates the successful application of phosphonate-anchored self-assembled monolayers (SAMs) as ultrathin coatings for such particles. It also describes a new chemical approach to the anchoring of antibodies on the surface of SAM-coated IONPs (using nucleophilic aromatic substitution). This anchoring strategy results in stable, nonhydrolyzable, covalent attachment and allows the reactivity of the particles toward antibody binding to be activated in situ, such that prior to the activation the modified surface is stable for long-term storage. While the SAMs do not have the well-packed crystallinity of other such monolayers, their structure was studied using smooth model substrates based on an iron oxide layer on a double-side polished silicon wafer. In this way, atomic force microscopy, ellipsometry, and contact angle goniometry (tools that could not be applied to the nanoparticles' surfaces) could contribute to the determination of their monomolecular thickness and uniformity. Finally, the successful conjugation of IgG antibodies to the SAM-coated IONPs such that the antibodies retain their biological activity is verified by their complexation to a secondary fluorescent antibody.

  15. Reaction of perfluoroalkyl grignard reagents with phosphorus trihalides: a new route to perfluoroalkyl-phosphonous and -phosphonic acids.

    Science.gov (United States)

    Hosein, Adil I; Le Goff, Xavier F; Ricard, Louis; Caffyn, Andrew J M

    2011-02-21

    The reaction of perfluoroalkyl Grignard reagents with phosphorus(III) halides was explored. In the process a new convenient, one-pot, high yield method for the synthesis of (perfluoroalkyl)phosphonic acids has been developed. Perfluoroalkyl Grignard reagents react with phosphorus trichloride or phosphorus tribromide to form (perfluoroalkyl)phosphonous dihalides. Hydrolysis gives the corresponding (perfluoroalkyl)phosphonous acids. Oxidation of the phosphonous acids with H(2)O(2) produces (perfluoroalkyl)phosphonic acids in 60-78% overall yields, based on the corresponding perfluoroalkyl iodide. The X-ray crystal structures of the toluidinium salts, [MeC(6)H(4)NH(3)](2)[C(2)F(5)PO(3)] and [MeC(6)H(4)NH(3)][C(8)F(17)P(O)(2)OH], are reported.

  16. Probing the interaction of U(vi) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy.

    Science.gov (United States)

    Uribe, Eva C; Mason, Harris E; Shusterman, Jennifer A; Bruchet, Anthony; Nitsche, Heino

    2016-06-21

    The fundamental interaction of U(vi) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(vi) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse (31)P NMR on U(vi) contacted samples revealed that U(vi) only interacts with a fraction of the ligands present on the surface. At pH 4 the U(vi) extraction capacity of the material is limited to 27-37% of the theoretical capacity, based on ligand loading. We combined single pulse (31)P NMR on U(vi)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(vi) binds to deprotonated phosphonate and/or silanol sites. We use (31)P-(31)P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(vi)-complexed and non-complexed ligand environments. These measurements reveal that U(vi) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.

  17. Reactivity of rhodium(I) complexes bearing nitrogen-containing ligands toward CH3I: synthesis and full characterization of neutral cis-[RhX(CO)2(L)] and acetyl [RhI(μ-I)(COMe)(CO)(L)]2 complexes.

    Science.gov (United States)

    Adcock, Romain J; Nguyen, Duc Hanh; Ladeira, Sonia; Le Berre, Carole; Serp, Philippe; Kalck, Philippe

    2012-08-20

    The neutral rhodium(I) square-planar complexes [RhX(CO)(2)(L)] [X = Cl (3), I (4)] bearing a nitrogen-containing ligand L [diethylamine (a), triethylamine (b), imidazole (c), 1-methylimidazole (d), pyrazole (e), 1-methylpyrazole (f), 3,5-dimethylpyrazole (g)] are straightforwardly obtained from L and [Rh(μ-X)(CO)(2)](2) [X = Cl (1), I (2)] precursors. The synthesis is extended to the diethylsulfide ligand h for 3h and 4h. According to the CO stretching frequency of 3 and 4, the ranking of the electronic density on the rhodium center follows the order b > a ≈ d > c > g > f ≈ h > e. The X-ray molecular structures of 3a, 3d-3f, 4a, and 4d-4f were determined. Results from variable-temperature (1)H and (13)C{(1)H} NMR experiments suggest a fluxional associative ligand exchange for 4c-4h and a supplementary hydrogen-exchange process in 4e and 4g. The oxidative addition reaction of CH(3)I to complexes 4c-4g affords the neutral dimeric iodo-bridged acetylrhodium(III) complexes [RhI(μ-I)(COCH(3))(CO)(L)](2) (6c-6g) in very good isolated yields, whereas 4a gives a mixture of neutral 6a and dianionic [RhI(2)(μ-I)(COCH(3))(CO)][NHMeEt(2)](2) and 4h exclusively provides the analogue dianionic complex with [SMeEt(2)](+) as the counterion. X-ray molecular structures for 6d(2) and 6e reveal that the two apical CO ligands are in mutual cis positions, as are the two apical d and e ligands, whereas isomer 6d(1) is centrosymmetric. Further reactions of 6d and 6e with CO or ligand e gave quantitatively the monomeric complexes [RhI(2)(COCH(3))(CO)(2)(d)] (7d) and [RhI(2)(COCH(3))(CO)(e)(2)] (8e), respectively, as confirmed by their X-ray structures. The initial rate of CH(3)I oxidative addition to 4 as determined by IR monitoring is dependent on the nature of the nitrogen-containing ligand. For 4a and 4h, reaction rates similar to those of the well-known rhodium anionic [RhI(2)(CO)(2)](-) species are observed and are consistent with the formation of this intermediate species

  18. The enzymatic conversion of phosphonates to phosphate by bacteria.

    Science.gov (United States)

    Kamat, Siddhesh S; Raushel, Frank M

    2013-08-01

    Phosphonates are ubiquitous organophosphorus compounds that contain a characteristic CP bond which is chemically inert and hydrolytically stable. Bacteria have evolved pathways to metabolize these phosphonate compounds and utilize the products of these pathways as nutrient sources. This review aims to present all of the known bacterial enzymes capable of transforming phosphonates to phosphates. There are three major classes of enzymes known to date performing such transformations: phosphonatases, the C-P lyase complex and an oxidative pathway for CP bond cleavage. A brief description of each class is presented.

  19. Surface Modification of SnO2 with Phosphonic Acids

    Directory of Open Access Journals (Sweden)

    Ramona Gheonea

    2017-01-01

    Full Text Available The aim of the present work was the study of phosphonic acids grafting on the surface of SnO2 at different molar ratios. In this paper we describe the functionalization of SnO2 surfaces with phosphonic acids RPO(OH2. The surface modification process was achieved by using phenyl-phosphonic acid (PPA and vinyl-phosphonic acid (VPA. The synthesized materials were investigated by using FT-IR, TGA (in air and in nitrogen, EDX, ESEM, and TEM methods. This synthetic approach has many advantages: films with optical quality and controlled thickness can be obtained using low temperatures and cheap raw materials, by using “green chemistry” synthetic routes. The hybrid materials have structures diversity and fascinating applications, attracting attention for a long time, due to their potential.

  20. Chemoselective recognition with phosphonate cavitands: the ephedrine over pseudoephedrine case.

    Science.gov (United States)

    Biavardi, Elisa; Ugozzoli, Franco; Massera, Chiara

    2015-02-25

    Complete discrimination of ephedrine and pseudoephedrine, both in solution and in the solid state, was achieved with a phosphonate cavitand receptor. The molecular origin of the epimer discrimination was revealed by the crystal structure of the respective complexes.

  1. Synthesis of phosphonate and phostone analogues of ribose-1-phosphates

    Directory of Open Access Journals (Sweden)

    Pitak Nasomjai

    2009-07-01

    Full Text Available The synthesis of phosphonate analogues of ribose-1-phosphate and 5-fluoro-5-deoxyribose-1-phosphate is described. Preparations of both the α- and β-phosphonate anomers are reported for the ribose and 5-fluoro-5-deoxyribose series and a synthesis of the corresponding cyclic phostones of each α-ribose is also reported. These compounds have been prepared as tools to probe the details of fluorometabolism in S. cattleya.

  2. Synthesis of phosphonate and phostone analogues of ribose-1-phosphates.

    Science.gov (United States)

    Nasomjai, Pitak; O'Hagan, David; Slawin, Alexandra M Z

    2009-07-27

    The synthesis of phosphonate analogues of ribose-1-phosphate and 5-fluoro-5-deoxyribose-1-phosphate is described. Preparations of both the alpha- and beta-phosphonate anomers are reported for the ribose and 5-fluoro-5-deoxyribose series and a synthesis of the corresponding cyclic phostones of each alpha-ribose is also reported. These compounds have been prepared as tools to probe the details of fluorometabolism in S. cattleya.

  3. Neutral penta- and hexacoordinate silicon(IV) complexes containing two bidentate ligands derived from the alpha-amino acids (S)-alanine, (S)-phenylalanine, and (S)-tert-leucine.

    Science.gov (United States)

    Cota, Smaranda; Beyer, Matthias; Bertermann, Rüdiger; Burschka, Christian; Götz, Kathrin; Kaupp, Martin; Tacke, Reinhold

    2010-06-11

    The neutral hexacoordinate silicon(IV) complex 6 (SiO(2)N(4) skeleton) and the neutral pentacoordinate silicon(IV) complexes 7-11 (SiO(2)N(2)C skeletons) were synthesized from Si(NCO)(4) and RSi(NCO)(3) (R = Me, Ph), respectively. The compounds were structurally characterized by solid-state NMR spectroscopy (6-11), solution NMR spectroscopy (6 and 10), and single-crystal X-ray diffraction (8 and 11 were studied as the solvates 8 x CH(3)CN and 11 x C(5)H(12) x 0.5 CH(3)CN, respectively). The silicon(IV) complexes 6 (octahedral Si-coordination polyhedron) and 7-11 (trigonal-bipyramidal Si-coordination polyhedra) each contain two bidentate ligands derived from an alpha-amino acid: (S)-alanine, (S)-phenylalanine, or (S)-tert-leucine. The deprotonated amino acids act as monoanionic (6) or as mono- and dianionic ligands (7-11). The experimental investigations were complemented by computational studies of the stereoisomers of 6 and 7.

  4. Role of Citrate Ions in the Phosphonate-based Inhibitor System for Mild Steel in Aqueous Chloride Media

    Directory of Open Access Journals (Sweden)

    G. Gunasekaran

    2005-01-01

    Full Text Available The corrosion inhibition efficiency of phosphonic acid and its derivatives for the inhibition of corrosion of mild steel in neutral chloride media is decided by its ability to form protectivefilm over the surface. In this context, the effect of addition of metal cations and certain organic compounds, such as citrate in conjugation with phosphonic acid to impart synergistic corrosion inhibition has been explored. The experiments were carried out using various concentrations of trisodium citrate and zinc ions in an aqueous solution of 2-carboxyethyl phosphonic acid (2CEPA at 25 ppm. The corrosion characteristics have been determined using electrochemical impedance spectroscopy together with determination of corrosion rate by weight-loss method. It has been observed that a combination of inhibitive ions, namely citrate, ZCEPA, and zinc ions at 25 ppm gives 96 per cent inhibition efficiency and this corrosion inhibition is due to the formation of a protective film. By increasing the concentration of citrate beyond 25 ppm, the corrosion inhibition efficiency decreases. This paper discusses the role of citrate and zinc ions in imparting added corrosion inhibition ability using 2CEPA on the basis of experimental results.

  5. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: Synthesis, characterization, fluorescence and corrosion inhibitors of ligands

    Science.gov (United States)

    Ali, Omyma A. M.

    2014-11-01

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans.

  6. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

    Science.gov (United States)

    Ali, Omyma A M

    2014-11-11

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans.

  7. Synthesis, spectroscopic characterization and solution behavior of new tin tetrachloride adducts with γ-keto allyl phosphonates

    Science.gov (United States)

    Elleuch, Haitham; Sanhoury, M. A. K.; Rezgui, F.

    2017-01-01

    Four new octahedral complexes of the type [SnCl4L2] (L = γ-keto allyl phosphonate) (1-4) were prepared and characterized by multinuclear (1H, 13C, 31P and 119Sn) NMR, IR spectroscopy and elemental analysis. The NMR data show, as expected, that these complexes exist in solution as mixtures of cis and trans isomers. More importantly, the solution structure was confirmed by 119Sn NMR spectra which show two triplets corresponding to the two isomers. In addition, the solution behavior of these complexes in the presence of excess ligand was studied by variable temperature NMR using the coalescence temperature method. The metal-ligand exchange activation energies were therefore determined and found to be in the range 57-60 kJ/mol. The effect of remote substituents on the metal-ligand interaction was studied and compared with closely related tin-phosphoryl complexes.

  8. Synthesis of Peptidomimetic Conjugates of Acyclic Nucleoside Phosphonates

    Science.gov (United States)

    Serpi, Michaela; Zakharova, Valeria M.; Krylov, Ivan S.; McKenna, Charles E.

    2010-01-01

    Cyclic nucleoside phosphonates connected through a P-O-C linkage to a promoiety represent a class of prodrugs designed to overcome the low oral bioavailability of parent antiviral acyclic nucleoside phosphonates. In our prodrug approach, a non-toxic promoiety such as an amino acid or dipeptide is conjugated to the cyclic form of the parent drug by esterification of the phosphonic acid moiety by an alcoholic amino acid side chain (Ser, Tyr, and analogues) or through a glycol linker. For the biological evaluation and investigation of the pharmacokinetic profiles of these modified nucleoside phosphonates, a reliable synthetic procedure that allows preparation of sufficient amount of potential prodrugs is needed. This unit describes a method for generating peptidomimetic conjugates of two potent antiviral acyclic nucleoside phosphonates: 1-[(2S)-3-hydroxy-2-phosphonomethoxypropyl]cytosine ((S)-HPMPC, and 9-[(2S)-3-hydroxy-2-phosphonomethoxypropyl]adenine ((S)-HPMPA). Two alternate strategies allowing synthesizing selected amino acid, dipeptide, or ethylene glycol-linked amino acid prodrugs of (S)-HPMPC and (S)-HPMPA in solution and using a solid-phase approach are presented. PMID:21154529

  9. Hydroformylation of olefins with cobalt/phosphonate- and cobalt/sufonate-phosphines

    Energy Technology Data Exchange (ETDEWEB)

    Martin, A.; Kant, M. [Leibniz-Institut fuer Katalyse e.V., Berlin (Germany); Giuffrida, G.; Rosano, S. [Sasol Italy S.p.A., Paderno Dugnano (Italy)

    2006-07-01

    The hydroformylation of an industrial decene mixture with cobalt/phosphonate- and cobalt/sulfonate-phosphines used as catalysts was carried out. Highest aldehyde yield of ca. 60-65 mol% beside 2-5 mol% decane, 1-5 mol% decenes and 2-5 mol% of other oxoproducts was obtained at 170 C, 160-200 bar syngas pressure and a reaction time of 12-16 h. The reminder is a fraction of non-GC-detectable heavy oligomers (15-20 %). Best olefin conversion was reached with Ph{sub 2}P(p-C{sub 6}H{sub 4}-SO{sub 3}Li) and TPPTS as ligands, best stability of biphasic system with TPPTS and Ph{sub 2}P-(CH{sub 2}){sub 3}-SO{sub 3}Li. The terminal aldehyde selectivity amounted to 36-42 mol% of the aldehyde pool. (orig.)

  10. Syntheses and structural characterization of iron(II) and copper(II) coordination compounds with the neutral flexible bidentate N-donor ligands

    Science.gov (United States)

    Beheshti, Azizolla; Lalegani, Arash; Bruno, Giuseppe; Rudbari, Hadi Amiri

    2014-08-01

    Two new coordination compounds [Fe(bib)2(N3)2]n(1) and [Cu2(bpp)2(N3)4] (2) with azide and flexible ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp) were prepared and structurally characterized. In the 2D network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while in the dinuclear structure of 2, the copper(II) ion adopts an FeN5 distorted square pyramid geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to copper(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied.

  11. Synthesis and stereochemistry of 6-membered ring phosphonates

    Directory of Open Access Journals (Sweden)

    Michael D. Pungente

    2012-03-01

    Full Text Available Background: Organophosphorus compounds have important industrial and biomedical applications as pharmaceutical and agrochemical agents, as well as transition state analogs for the production of monoclonal antibodies. Methods: Two diastereomers of a 6-membered ring, cyclic phenyl phosphonate were synthesized in 8 steps from 1,3-butanediol. Results: The stereochemistry of the diastereomers was elucidated on the basis of H NMR nuclear Overhauser effects (NOE difference experiments. Conclusions: Such cyclic phosphonates may have utility serving as transition state analogs for the production of monoclonal antibodies.

  12. XPS investigation of DNA binding to zirconium-phosphonate surfaces.

    Science.gov (United States)

    Lane, Sarah M; Monot, Julien; Petit, Marc; Bujoli, Bruno; Talham, Daniel R

    2007-07-01

    The surface coverage of phosphorylated oligonucleotides immobilized on a zirconium-phosphonate surface was analyzed using X-ray photoelectron spectroscopy (XPS). By quantifying the intensity of the N 1s signal originating from the oligonucleotide and the Zr 3d peak from the metal-phosphonate surface, the surface coverage of the oligonucleotide could be calculated with a modified substrate-overlayer model. We found relatively low surface coverages indicating that once covalently bound via the terminal phosphate the polymer chain further physisorbs to the surface limiting the adsorption of additional molecules.

  13. New water soluble phosphonate and polycarboxylate complexants for enhanced f element separations

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L.; Rickert, P.G.; Lessmann, E.P.; Mendoza, M.D.; Feil, J.F.; Sullivan, J.C.

    1994-08-01

    While lipophilic extractant molecules and ion exchange polymeric materials are clearly essential to efficient separation of metal ions by solvent extraction or ion exchange, the most difficult separations often could not be accomplished without the use of water soluble complexants. This report focuses on recent developments in design, synthesis and characterization of phosphonic acid and polycarboxylic acid ligands for enhanced f element separations. Emphasis is on the basic solution chemistry and crystal structures of complexes of the f elements with selected amino-derivatives of methanediphosphonic acid and with tetrahydrofuran-2,3,4,5-tetracarboxylic acid. The former series of compounds exhibit high affinity for lanthanides and actinides in acidic solutions. The latter ligand exhibits an unusual (and very useful) ``anti-selectivity`` for uranyl ion in a solvent extraction process, which permits efficient separation of uranyl from more radioactive components of nuclear wastes. Most of the observed effects can be explained through examination of the structure of the ligand, and comparison of the spectroscopic and thermodynamic parameters for complexation of various metal ions.

  14. Water wafers: structure and melting of a hydrate inclusion compound of a neutral Pt(IV) complex with 1-methylcytosinato ligands

    Science.gov (United States)

    Randaccio, Lucio; Zangrando, Ennio; Cesàro, Attilio; Holthenrich, Dagmar; Lippert', Bernhard

    1998-01-01

    The characterization by X-ray analysis of the trans, trans, trans-[bis(1-methylcytosinate, N4)bis(ammine)bis(hydroxo)platinum(IV)] octahydrate complex (I) reveals an unexpected crystal packing. The neutral complex molecule is hosted by layers, totally built up by water molecules which do not exhibit a direct coordination to metal ions. These corrugated layers are made by puckered eight- and planar four-membered rings of water molecules, held together by hydrogen bonds with an ordered proton arrangement.

  15. A Multifunctional Mn(II) Phosphonate for Rapid Separation of Methyl Orange and Electron-Transfer Photochromism.

    Science.gov (United States)

    Gao, Chao-Ying; Yang, Yang; Ai, Jing; Tian, Hong-Rui; Li, Lei-Jiao; Yang, Weiting; Dang, Song; Sun, Zhong-Ming

    2016-08-08

    A Mn(II) phosphonate of the general formula [Mn(H2 L)2 (H2 O)2 (H2 bibp)] adopts a layered motif with protonated H2 bibp(2+) cations embedded in the channels (H4 L=thiophene-2-phosphonic acid; bibp=4,4'-bis(1-imidazolyl)biphenyl). The title compound exhibits excellent adsorptive removal of methyl orange (MO) dye from aqueous solution. Its advantageous features include fast adsorption, high uptake capacity, selective removal, and reusability, which are of great significance for practical application in wastewater treatment. Meanwhile, the compound displays rapid photochromism upon irradiation with visible light at room temperature. Extensive research has demonstrated that such behavior is based on a ligand-to-ligand charge-transfer (LLCT) mechanism. The irradiated sample possesses an ultra-long-lived charge-separated state. Moreover, not only is the compound the first Mn-based photochromic MOF, but it is also one of the very few examples showing LLCT with non-photochromic components. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A functionalized phosphonate-rich organosilica layered hybrid material (PSLM) fabricated through a mild process for heavy metal uptake

    Energy Technology Data Exchange (ETDEWEB)

    Daikopoulos, Chris [Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110 (Greece); Bourlinos, Athanasios B. [Institute of Materials Science, NCSR “Demokritos”, Ag. Paraskevi Attikis, Athens 15310 (Greece); Georgiou, Yiannis [Laboratory of Physical Chemistry, Department of Environmental and Natural Resources Management, University of Patras, Seferi 2, Agrinio 30100 (Greece); Deligiannakis, Yiannis, E-mail: ideligia@cc.uoi.gr [Laboratory of Physical Chemistry, Department of Environmental and Natural Resources Management, University of Patras, Seferi 2, Agrinio 30100 (Greece); Zboril, Radek [Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry and Experimental Physics, Palacky University, Olomouc 77146 (Czech Republic); Karakassides, Michael A. [Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110 (Greece)

    2014-04-01

    Highlights: • Novel phosphonate-rich organosilica layered hybrid material (PSLM) fabricated through a mild xerogel process. • Surface Complexation Modeling reveals that PSLM bears 2 types of functional groups able to bind heavy metal. • Maximum metal uptake capacities were found 2.72 mmol g{sup −1} for Cu{sup 2+}, 1.67 mmol g{sup −1} for Pb{sup 2+} and 1.00 mmol g{sup −1} for Cd{sup 2+} at pH 7. • EPR spectroscopy reveals local coordination environment for Cu{sup 2+} ions. - Abstract: A phosphonate-rich organosilica layered hybrid material (PSLM) made of 3-(trihydroxysilyl)propyl methylphosphonate, monosodium salt, as the single silica source, has been obtained from its aqueous solution through a xerogel process and mild thermal aging. The method is simple, affording bulk quantities of powdered PSLM in a single-step. The hybrid is stable in water and possesses a high content of phosphonate groups fixed on the solid matrix. In addition, PSLM shows good thermal stability, which exceeds 300 °C in air. The material was characterized using SEM, TEM, XRD, FT-IR and TGA techniques. Potentiometric titrations show that PSLM bears high-surface density of phosphonate groups (3 mmol g{sup −1}). As a result, the material displays high metal uptake capacity for heavy metal ions such as Cu{sup 2+} (2.72 mmol g{sup −1}), Pb{sup 2+} (1.67 mmol g{sup −1}) and Cd{sup 2+} (1.00 mmol g{sup −1}) at neutral pH values e.g. the pH of natural waters. Detailed theoretical modeling using a Surface Complexation Model combined with Electron Paramagnetic Resonance (EPR) spectroscopy shows that the surface distribution of surface bound Cu{sup 2+} ions is rather homogeneous e.g. copper-binding phosphonate sites are arranged in average distances 5–8 Å.

  17. Adsorption and separation of organic six-membered ring analogues on neutral Cd(II)-MOF generated from asymmetric schiff-base ligand.

    Science.gov (United States)

    Duan, Li; Wu, Zhen-Hua; Ma, Jian-Ping; Wu, Xiang-Wen; Dong, Yu-Bin

    2010-12-06

    A new CdL(2)-MOF was synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. A series of organic six-membered ring analogues, namely, 1,4-dioxane, cyclohexane, cyclohexene, benzene, cyclohexanone, and cyclohexanol, can be absorbed by the CdL(2) porous framework in liquid-phase to generate G(n)⊂CdL(2) (n = 1 and 2) host-guest complexes. In addition, the CdL(2) host framework displays different affinity for these six-membered ring substrates and can effectively separate them under mild conditions (i.e., 1, 4-dioxane > cyclohexane > cyclohexene and benzene > cyclohexanone > cyclohexanol). The empty CdL(2) displays strong green-yellow emission. Furthermore, these host-guest systems show an interesting guest-driven luminescent emission, and the emission intensities of these guest-loaded complexes are effectively reduced.

  18. Amberlyst-15 catalyzed synthesis of alkyl/aryl/heterocyclic phosphonates

    Institute of Scientific and Technical Information of China (English)

    U.M. Rao Kunda; V.N. Reddy Mudumala; C.S. Reddy Gangireddy; B.R. Nemallapudi; K.N. Sandip; S.R. Cirandur

    2011-01-01

    A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and tri-alkyl/aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditions was applied. It demonstrated several advantages such as good yields of products, simple operation, convenient separation and inexpensive catalyst.

  19. Synthesis of biologically active phosphonates from Lesquerella oil

    Science.gov (United States)

    Bisphosphonates and vinyl phosphonates are two classes of compounds that have much potential, namely as pharmaceutical agents and synthetic building blocks. Previous studies have shown success in synthesizing these compounds from hydroxy fatty acids (HFAs) found in Ricinus communis, commonly known a...

  20. PEG-bis phosphonic acid based ionic supramolecular structures

    DEFF Research Database (Denmark)

    Gonzalez, Lidia; Skov, Anne Ladegaard; Hvilsted, Søren

    2014-01-01

    A number of supramolecular structures are prepared by mixing stoichiometric amounts of a phosphonic acid terminated poly(ethylene glycol) with propargyl amine, hexamethylene diamine, tris(2-aminoethyl)amine, and the first generation of a poly(propylene imine) dendrimer in turn at room temperature...

  1. Comparison of different phosphorus-containing ligands complexing {sup 68}Ga for PET-imaging of bone metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Fellner, M.; Riss, P.; Loktionova, N.; Zhernosekov, K.; Roesch, F. [Univ. of Mainz, Inst. of Nuclear Chemistry, Mainz (Germany); Thews, O. [Univ. of Mainz, Inst. of Pathophysiology, Mainz (Germany); Geraldes, C.F.G.C. [Univ. of Coimbra, Faculty of Science and Technology, and Center of Neurosciences and Cell Biology, Dept. of Life Science, Coimbra (Portugal); Kovacs, Z. [Univ. of Texas Southwestern Medical Center, Advanced Imaging Research Center, Dallas, TX (United States); Lukes, I. [Charles Univ., Dept. of Inorganic Chemistry, Prague (Czech Republic)

    2011-07-01

    {sup 99m}Tc-phosphonate structures are well established tracers for bone tumour imaging. Our objective was to investigate different {sup 68}Ga-labelled phosphonate ligands concerning labelling kinetics, binding to hydroxyapatite and bone imaging using {mu}-PET. Seven macrocyclic phosphorus-containing ligands and EDTMP were labelled in nanomolar scale with n.c.a. {sup 68}Ga in Na-HEPES buffer at pH{proportional_to}4. Except for DOTP, all ligands were labelled with >92% yield. Binding of the {sup 68}Ga-ligand complexes on hydroxyapatite was analysed to evaluate the effect of the number of the phosphorus acid groups on adsorption parameters. Adsorption of {sup 68}Ga-EDTMP and 68Ga-DOTP was >83%. For the {sup 68}Ga-NOTA-phosphonates an increasing binding with increasing number of phosphonate groups was observed but was still lower than {sup 68}Ga-DOTP and {sup 68}Ga-EDTMP. {mu}-PET studies in vivo were performed with {sup 68}Ga-EDTMP and {sup 68}Ga-DOTP with Wistar rats. While {sup 68}Ga-EDTMP-PET showed uptake on bone structures, an excess amount of the ligand (>1.5 mg EDTMP/kg body weight) had to be used, otherwise the {sup 68}Ga{sup 3+} is released from the complex and forms gallium hydroxide or it is transchelated to {sup 68}Ga-transferrin. As a result, the main focus of further phosphonate structures has to be on complex formation in high radiochemical yields with macrocyclic ligands with phosphonate groups that are not required for complexing {sup 68}Ga. (orig.)

  2. Limited Neutrality

    DEFF Research Database (Denmark)

    Nielsen, Morten Ebbe Juul

    2006-01-01

    Article Concerning the prospect of a kind of limited neutrality in place of the standard liberal egalitarian "neutrality of justification."......Article Concerning the prospect of a kind of limited neutrality in place of the standard liberal egalitarian "neutrality of justification."...

  3. Limited Neutrality

    DEFF Research Database (Denmark)

    Nielsen, Morten Ebbe Juul

    2006-01-01

    Article Concerning the prospect of a kind of limited neutrality in place of the standard liberal egalitarian "neutrality of justification."......Article Concerning the prospect of a kind of limited neutrality in place of the standard liberal egalitarian "neutrality of justification."...

  4. Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

    Science.gov (United States)

    Zheng, Tao; Yang, Zaixing; Gui, Daxiang; Liu, Zhiyong; Wang, Xiangxiang; Dai, Xing; Liu, Shengtang; Zhang, Linjuan; Gao, Yang; Chen, Lanhua; Sheng, Daopeng; Wang, Yanlong; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

    2017-05-01

    Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. Herein, we overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. These compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.

  5. Phosphonate molecular layers on TiO2 surfaces

    Directory of Open Access Journals (Sweden)

    Canepa P.

    2017-01-01

    Full Text Available We investigated the deposition of (HO2-PO-S-(CH215-COOH on TiO2. The phosphonate group has been chosen to serve as the anchoring moiety while the carboxylic group can be exploited for further coupling with antibacterial peptides. Native oxide-covered polished Ti samples were used as substrates for the molecular deposition. Previous to deposition, the substrates were plasma-cleaned in order to enrich their surfaces of hydroxyl groups, suitable for phosphonate coupling. The combined analysis of atomic force microscopy, X-ray photoemission spectroscopy and differential spectroscopic ellipsometry measurements indicates the formation of a submonolayer film made of irregular islands, one molecule thick.

  6. Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

    Science.gov (United States)

    2016-01-01

    Summary Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given. PMID:27559377

  7. Characterisation of Campylobacter jejuni genes potentially involved in phosphonate degradation

    Directory of Open Access Journals (Sweden)

    Hartley Lauren E

    2009-06-01

    Full Text Available Abstract Potential biological roles of the Campylobacter jejuni genes cj0641, cj0774c and cj1663 were investigated. The proteins encoded by these genes showed sequence similarities to the phosphonate utilisation PhnH, K and L gene products of Escherichia coli. The genes cj0641, cj0774c and cj1663 were amplified from the pathogenic C. jejuni strain 81116, sequenced, and cloned into pGEM-T Easy vectors. Recombinant plasmids were used to disrupt each one of the genes by inserting a kanamycin resistance (KmR cassette employing site-directed mutagenesis or inverse PCR. Campylobacter jejuni 81116 isogenic mutants were generated by integration of the mutated genes into the genome of the wild-type strain. The C. jejuni mutants grew on primary isolation plates, but they could not be purified by subsequent passages owing to cell death. The mutant C. jejuni strains survived and proliferated in co-cultures with wild-type bacteria or in media in which wild-type C. jejuni had been previously grown. PCR analyses of mixed wild-type/mutant cultures served to verify the presence of the mutated gene in the genome of a fraction of the total bacterial population. The data suggested that each mutation inactivated a gene essential for survival. Rates of phosphonate catabolism in lysates of E. coli strain DH5α were determined using proton nuclear magnetic resonance spectroscopy. Whole-cell lysates of the wild-type degraded phosphonoacetate, phenylphosphonate and aminomethylphosphonate. Significant differences in the rates of phosphonate degradation were observed between lysates of wild-type E. coli, and of bacteria transformed with each one of the vectors carrying one of the C. jejuni genes, suggesting that these genes were involved in phosphonate catabolism.

  8. Phosphonic Acid-Functionalized Polyurethane Dispersions with Improved Adhesion Properties.

    Science.gov (United States)

    Breucker, Laura; Landfester, Katharina; Taden, Andreas

    2015-11-11

    A facile route to phosphorus-functionalized polyurethane dispersions (P-PUDs) with improved adhesion properties is presented. (Bis)phosphonic acid moieties serve as adhesion promoting sites that are covalently attached via an end-capping reaction to isocyanate-reactive polyurethane particles under aqueous conditions. The synthetic approach circumvents solubility issues, offers great flexibility in terms of polyurethane composition, and allows for the synthesis of semicrystalline systems with thermomechanical response due to reversible physical cross-linking. Differential scanning calorimetry (DSC) is used to investigate the effect of functionalization on the semicrystallinity. The end-capping conversion was determined via inductively-coupled plasma optical emission spectroscopy (ICP-OES) and was surprisingly found to be almost independent of the stoichiometry of reaction, suggesting an adsorption-dominated process. Particle charge detection (PCD) experiments reveal that a dense surface coverage of phosphonic acid groups can be attained and that, at high functionalization degrees, the phosphonic adhesion moieties are partially dragged inside the colloidal P-PUD particle. Quartz crystal microbalance with dissipation (QCMD) investigations conducted with hydroxyapatite (HAP) and stainless steel sensors as model surfaces show a greatly enhanced affinity of the aqueous P-PUDs and furthermore indicate polymer chain rearrangements and autonomous film formation under wet conditions. Due to their facile synthesis, significantly improved adhesion, and variable film properties, P-PUD systems such as the one described here are believed to be of great interest for multiple applications, e.g., adhesives, paints, anticorrosion, or dentistry.

  9. Probing the influence of phosphonate bonding modes to uranium(VI) on structural topology and stability: a complementary experimental and computational investigation.

    Science.gov (United States)

    Zheng, Tao; Wu, Qun-Yan; Gao, Yang; Gui, Daxiang; Qiu, Shiwen; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Shi, Wei-Qun; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-04-20

    Systematic control of the reactions between U(VI) and 1,4-phenylenebis(methylene))bis(phosphonic acid) (pmbH4) allows for alterations in the bonding between these constituents and affords three uranyl phosphonate compounds with chiral one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) structures, namely, [TPA][UO2(pmbH3)(pmbH2)H2O]·2H2O (1), [NH4]2[UO2(pmb)] (2), UO2(pmbH2) (3), and the first uranyl mixed phosphite/phosphonate compound [TMA]2[(UO2)2(pmb)(HPO3)] (4) (TPA = NPr4+, TMA = NMe4+). These compounds crystallize in the space groups P212121, P1̅, P21/c, and Cmcm, respectively. Further investigation of the local uranyl coordination environment reveals that in 1 only oxygen atoms from P=O moieties ligate the uranium centers; whereas in 2 only P-O(-) oxygen atoms are involved in bonding and yield a layered topology. Compound 3 differs sharply from the first two in that conjugated P=O and P-O(-) oxygen atoms chelate the uranium centers resulting in a 3D framework. In compound 4, a phosphonate group bridges three uranyl centers further coordinated with a phosphite ligand HPO32–, which is a product of pmbH4 decomposing, forming a 2D layered structure. Compounds 3 and 4 also contain a different coordination environment for U(VI) than that found in 1 or 2. In this case, tetragonal bipyramidal UO6 units occur instead of the far more common UO7 pentagonal bipyramids found in 1 and 2. Interestingly, 1 converts to 3 at elevated reaction temperatures, indicating that the formation of 1 is likely under kinetic control. This is supported by thermal analysis, which reveals that 3 has higher thermal stability than 1 or 2. UV-vis-near-IR absorption and fluorescence spectroscopy show that the absorption and photoluminescence intensity increases from 1 to 4. Density functional theory electronic structure calculations provide insight into the nature of the interactions between U(VI) and the phosphonate ligands.

  10. Copper-catalyzed α-amination of phosphonates and phosphine oxides: a direct approach to α-amino phosphonic acids and derivatives.

    Science.gov (United States)

    McDonald, Stacey L; Wang, Qiu

    2014-02-10

    A direct approach to important α-amino phosphonic acids and its derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of CN bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope.

  11. Designable architectures on nanoparticle surfaces: zirconium phosphate nanoplatelets as a platform for tetravalent metal and phosphonic acid assemblies.

    Science.gov (United States)

    Mosby, Brian M; Goloby, Mark; Díaz, Agustín; Bakhmutov, Vladimir; Clearfield, Abraham

    2014-03-11

    Surface-functionalized zirconium phosphate (ZrP) nanoparticles were synthesized using a combination of ion exchange and self-assembly techniques. The surface of ZrP was used as a platform to deposit tetravalent metal ions by direct ion exchange with the protons of the surface phosphate groups. Subsequently, phosphonic acids were attached to the metal ion layer, effectively functionalizing the ZrP nanoparticles. Use of axially oriented bisphosphonic acids led to the ability to build layer-by-layer assemblies from the nanoparticle surface. Varying the metal ion and ligand used allowed designable architectures to be synthesized on the nanoparticle surface. X-ray powder diffraction, XPS, electron microprobe, solid-state NMR, FTIR, and TGA were used to characterize the synthesized materials.

  12. Phosphonate removal from discharged circulating cooling water using iron-carbon micro-electrolysis.

    Science.gov (United States)

    Zhou, Zhen; Qiao, Weimin; Lin, Yangbo; Shen, Xuelian; Hu, Dalong; Zhang, Jianqiao; Jiang, Lu-Man; Wang, Luochun

    2014-01-01

    Phosphonate is a commonly used corrosion and scale inhibitor for a circulating cooling water (CCW) system. Its discharge could cause eutrophication of receiving waters. The iron-carbon (Fe/C) micro-electrolysis technology was used to degrade and remove phosphonate from discharged CCW. The influences of initial pH, Fe/C ratio (FCR) and temperature on phosphonate removal were investigated in a series of batch tests and optimized by response surface methodology. The quadratic model of phosphonate removal was obtained with satisfactory degrees of fitness. The optimum conditions with total phosphorus removal efficiency of 95% were obtained at pH 7.0, FCR of 1.25, and temperature of 45 °C. The phosphonate removal mechanisms were also studied. Phosphonate removal occurred predominantly via two consecutive reactive phases: the degradation of phosphonate complexes (Ca-phosphonate) and the precipitation of Fe/C micro-electrolysis products (PO₄(3-), Ca²⁺ and Fe³⁺).

  13. Novel and Convenient Approach to Synthesis of AZT/d4T H-phosphonates

    Institute of Scientific and Technical Information of China (English)

    LIN, Chang-Xue(林长学); FU, Hua(付华); TU, Guang-Zhong(涂光忠); ZHAO, Yu-Fen(赵玉芬)

    2004-01-01

    A convenient, efficient and general method has been developed for synthesis of H-phosphonate mono and diesters of AZT and d4T through one-pot reaction of phosphonic acid with AZT or d4T and different alcohols using pivaloyl chloride as condensing agent under mild conditions.

  14. A New Epoxy Bis-Phosphonate Crosslinker for Durable Fire Retardancy on Cotton

    Science.gov (United States)

    A new epoxy bis-phosphonate crosslinker for cotton [2-(dimethoxy-phosphorylmethyl)-oxiranylmethyl]-phosphonic acid dimethyl ester was prepared in two steps from 3-chloro-2-chloromethylpropene in 55% yield. The new monomer was characterized by proton and carbon NMR and GC-mass spectrometry. This cro...

  15. Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

    Energy Technology Data Exchange (ETDEWEB)

    Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K. [Sungkyunkwan Univ., Suwon (Korea, Republic of). Dept. of Energy Science; Rao, C.V.S. Brahmmananda; Jayalakshmi, S. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2015-06-01

    The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

  16. Structural variations in layered alkaline earth metal cyclohexyl phosphonates

    Indian Academy of Sciences (India)

    Ramaswamy Murugavel; Nayanmoni Gogoi

    2009-06-01

    Two series of alkaline earth metal cyclohexyl phosphonates, M(C6H11PO3H)2(H2O) (M = Ca, Sr and Ba) (1–3) and M(C6H11PO3)(H2O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray diffraction techniques. The molecular structure of compound 2 determined using single crystal X-ray diffraction technique reveals a layered polymeric structure.

  17. EVALUATION OF ANTIBACTERIAL ACTIVITIES OF NOVEL AZIRIDINYL PHOSPHONATES

    Directory of Open Access Journals (Sweden)

    Assia Keniche

    2016-05-01

    Full Text Available A new series of aziridines was synthesized in our laboratory, which displays potent antibiotic activities. However, a practical synthesis by using the coupling method of this aziridines with either phosphonate or N-phtaloyl acide moiety can be converted into various derivatives. This work describes new results of our ongoing research targeting new derivatives of biological interest. All the compounds were screened for their antibacterial activity, they all showed comparable moderate to good growth inhibitory activity with reference to Tetracyclin and Gentamicin.

  18. Synthesis and structure of neutral double helicate

    Institute of Scientific and Technical Information of China (English)

    SU, Xun-Cheng; ZHOU, Zhi-Fen; ZHU, Shou-Rong; CHEN, Yun-Ti; LENG, Xue-Bing; WENG, Lin-Hong; LIN, Hua-Kuan

    2000-01-01

    A new approach to geaerating supramolecular architectures, based on easy-to-prepare sehiff base ligands, is described to gether with its application to the self-assembly of supramolecu lar neutral double helicates.

  19. Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

  20. STUDIES ON THE SORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR LANTHANUM

    Institute of Scientific and Technical Information of China (English)

    XiongChunhua; ChenYiyong; 等

    1998-01-01

    The influences of Medium pH,sorption temperature,sorption time,etc.on the sorption capacity of macroporous phosphonic acid resin for La3+ were determined.The sorption rate constant was k298=7.64×10-5 s-1. The complex ratio of phosphonic groups of the resin to La3+ was 3:1.The basic sorption parameters were determined. The sorption mechanism of macroporous phosphonic acid resin for La3+ was examined by chemical analysis and IR-spectrometry.

  1. Intermediates in the transformation of phosphonates to phosphate by bacteria.

    Science.gov (United States)

    Kamat, Siddhesh S; Williams, Howard J; Raushel, Frank M

    2011-11-16

    Phosphorus is an essential element for all known forms of life. In living systems, phosphorus is an integral component of nucleic acids, carbohydrates and phospholipids, where it is incorporated as a derivative of phosphate. However, most Gram-negative bacteria have the capability to use phosphonates as a nutritional source of phosphorus under conditions of phosphate starvation. In these organisms, methylphosphonate is converted to phosphate and methane. In a formal sense, this transformation is a hydrolytic cleavage of a carbon-phosphorus (C-P) bond, but a general enzymatic mechanism for the activation and conversion of alkylphosphonates to phosphate and an alkane has not been elucidated despite much effort for more than two decades. The actual mechanism for C-P bond cleavage is likely to be a radical-based transformation. In Escherichia coli, the catalytic machinery for the C-P lyase reaction has been localized to the phn gene cluster. This operon consists of the 14 genes phnC, phnD, …, phnP. Genetic and biochemical experiments have demonstrated that the genes phnG, phnH, …, phnM encode proteins that are essential for the conversion of phosphonates to phosphate and that the proteins encoded by the other genes in the operon have auxiliary functions. There are no functional annotations for any of the seven proteins considered essential for C-P bond cleavage. Here we show that methylphosphonate reacts with MgATP to form α-D-ribose-1-methylphosphonate-5-triphosphate (RPnTP) and adenine. The triphosphate moiety of RPnTP is hydrolysed to pyrophosphate and α-D-ribose-1-methylphosphonate-5-phosphate (PRPn). The C-P bond of PRPn is subsequently cleaved in a radical-based reaction producing α-D-ribose-1,2-cyclic-phosphate-5-phosphate and methane in the presence of S-adenosyl-L-methionine. Substantial quantities of phosphonates are produced worldwide for industrial processes, detergents, herbicides and pharmaceuticals. Our elucidation of the chemical steps for the

  2. The preparation of trisubstituted alkenyl nucleoside phosphonates under ultrasound-assisted olefin cross-metathesis.

    Science.gov (United States)

    Sari, Ozkan; Hamada, Manabu; Roy, Vincent; Nolan, Steven P; Agrofoglio, Luigi A

    2013-09-01

    Intermolecular ultrasound-assisted olefin cross-metathesis is reported. This approach allows an easy access to challenging trisubstituted alkenyl nucleoside phosphonates. Regioselective chemoenzymatic deacetylation and Mitsunobu coupling are also described.

  3. Preliminary assessment of developmental toxicity of Perfluorinated Phosphonic Acid in mice

    Science.gov (United States)

    Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These emerging chemicals have recently been detected in the environment, particularl...

  4. Washing powders and the environment: has TAED any influence on the complexing behaviour of phosphonic acids?

    Science.gov (United States)

    Deluchat, Véronique; Lacour, Stella; Serpaud, Bernard; Bollinger, Jean-Claude

    2002-10-01

    Complexation properties of two phosphonic acids: nitrilotris (methylenephosphonic acid) and 1-hydroxyethane-1,1'-diphosphonic acid, with Cu(II) and Ca(II) have been previously determined by pH and ionic selective electrode titrations. These phosphonic acids are commonly added to washing powders as polyphosphate substitutes and are here studied in the presence of another detergent compound: tetraacetylethylenediamine (TAED), a bleaching activator. Product concentrations were chosen in order to correspond to component concentration ratios encountered in washing powders. Potentiometric titrations were carried out to determine the possible TAED interferences; they indicate that TAED and its by-products have no action on phosphonic acid complexing behaviour. Under our experimental conditions, the action of TAED was modelled with acetic acid and ethylenediamine, the final by-products of TAED hydrolysis. If we take into account both phosphonic and acetic acids, speciation diagrams corresponding to representative fresh water systems showed that the acetic acid does not influence cation speciation.

  5. Synthesis and crystal structure of ethyl benzimidazole-2-yl phosphonate

    Institute of Scientific and Technical Information of China (English)

    HU, Fang-Zhong; WENG, Lin-Hong; YANG, Hua-Zheng; ZOU, Xiao-Mao

    2000-01-01

    When N-cyanoimido- ( O, O-diethyl ) phosphonyl/ S-methyl thiocarbonate (1) was treated with o-phenylenediamine in the presence of Et3N in ethanol, diethyl benzimidazole-2-yl recrys phonate(2) was obtained and hydrolyzed during the recrys tallization in MeOH/H2O, generating ethyl benzimidazole-2-yl phosphonate(3). The crystal structure of compound 3 was determined by X-ray diffraction method. The crystals belong to monoclinic, space rgoup C2/c, a=1.78408(18), b=O. 83725(9), c=1.67401(18) nm, β= 118.997(2)°, v=2. 1870(4) nm3, z=8, Dc=1.374g/cm3, F(000)=944.The final R and wR are 0.0499 and 0.1436, respectively. The mechanism of the above reaction is also discussed.

  6. Pillared metal(IV) phosphate-phosphonate extraction of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Burns, J.D.; Clearfield, A. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry; Borkowski, M.; Reed, D.T. [Los Alamos National Laboratory, Carlsbad, NM (United States). Earth and Environmental Sciences Div.

    2012-07-01

    Four pillared metal(IV) phosphate-phosphonate ion exchange materials were synthesized and characterized. Studies were conducted to determine their affinity for the lanthanides (Ln's) and actinides (An's). It was determined that by simply manipulating the metal source (Zr or Sn) and the phosphate source (H{sub 3}PO{sub 4} or Na{sub 3}PO{sub 4}) large differences were seen in the extraction of the Ln and An species. K{sub d} values higher than 4 x 10{sup 5} were observed for the AnO{sub 2}{sup 2+} species in nitric acid at pH 2. These basic uptake experiments are important, as the data they provide may indicate the possibility of a separation of Ln's from An's or even more notably americium from curium and Ln's. (orig.)

  7. ADSORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR INDIUM

    Institute of Scientific and Technical Information of China (English)

    WANG Huijun; XIONG Chunhua; YAO Caiping

    2004-01-01

    The adsorption kinetics and mechanism of a novel chelate resin, macroporous phosphonic acid resin (PAR) for In(III) were investigated. The statically saturated adsorption capacity is 216mg·g-1resin at 298K in HAc-NaAc medium. The apparent adsorption rate constant is k298=4.84×10-5 s-1. The adsorption behavior of PAR for In(III) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △H, free energy change △G and entropy change △S of PAR for In(III) are 11.5kJ/mol, -12.6kJ/mol and 80.8J/mol·K, respectively. The apparent activation energy is Ea=3.5kJ/mol. The molar coordination ratio of the functional group of PAR to In(III) is about 3∶1.

  8. Phosphonic acid functionalized poly(pentafluorostyrene) as polyelectrolyte membrane for fuel cell application

    Science.gov (United States)

    Atanasov, Vladimir; Oleynikov, Andrey; Xia, Jiabing; Lyonnard, Sandrine; Kerres, Jochen

    2017-03-01

    In this paper we introduce polyelectrolyte membranes based on phosphonated poly(pentafluorostyrene) (PPFS) and their performances in a fuel cell. The polyelectrolytes were obtained via partial phosphonation of PPFS varying the phosphonation degree from 17 to 66%. These membranes showed a high resistance to temperature (Tdecomp. = 355-381 °C) and radical attack (96-288 h in Fenton's test). A blend membrane consisting of 82 wt% fully phosphonated PPFS and 18 wt% poly(benzimidazole) is compared to the 66% phosphonated membrane having similar ion-conductivity (σ = 57 mS cm-1 at 120 °C, 90% RH). In the fuel cell the blend showed the best performance reaching 0.40 W cm-2 against 0.34 W cm-2 for the 42 wt% phosphonated membrane and 0.35 W cm-2 for Nafion 212. Furthermore, the blend maintained its operation at potentiostatic regime (0.5 V) for 620 h without declining in its performance. The highest power density of 0.78 W cm-2 was reached for the blend with a thickness of 15 μm using humidified oxygen (RH > 90%) at the cathode side. The switch from humidified to dry gasses during operation reduced the current density down to 0.6 A cm-2, but the cell maintained under operation for 66 h.

  9. Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: tracing sources and cycling of phosphonates.

    Science.gov (United States)

    Sandy, Edward H; Blake, Ruth E; Chang, Sae Jung; Jun, Yao; Yu, Chan

    2013-09-15

    The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the CP bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the CP bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: Tracing sources and cycling of phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: ruth.blake@yale.edu [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: yaojun@ustb.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)

    2013-09-15

    Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

  11. Discovery of phosphonic acid natural products by mining the genomes of 10,000 actinomycetes.

    Science.gov (United States)

    Ju, Kou-San; Gao, Jiangtao; Doroghazi, James R; Wang, Kwo-Kwang A; Thibodeaux, Christopher J; Li, Steven; Metzger, Emily; Fudala, John; Su, Joleen; Zhang, Jun Kai; Lee, Jaeheon; Cioni, Joel P; Evans, Bradley S; Hirota, Ryuichi; Labeda, David P; van der Donk, Wilfred A; Metcalf, William W

    2015-09-29

    Although natural products have been a particularly rich source of human medicines, activity-based screening results in a very high rate of rediscovery of known molecules. Based on the large number of natural product biosynthetic genes in microbial genomes, many have proposed "genome mining" as an alternative approach for discovery efforts; however, this idea has yet to be performed experimentally on a large scale. Here, we demonstrate the feasibility of large-scale, high-throughput genome mining by screening a collection of over 10,000 actinomycetes for the genetic potential to make phosphonic acids, a class of natural products with diverse and useful bioactivities. Genome sequencing identified a diverse collection of phosphonate biosynthetic gene clusters within 278 strains. These clusters were classified into 64 distinct groups, of which 55 are likely to direct the synthesis of unknown compounds. Characterization of strains within five of these groups resulted in the discovery of a new archetypical pathway for phosphonate biosynthesis, the first (to our knowledge) dedicated pathway for H-phosphinates, and 11 previously undescribed phosphonic acid natural products. Among these compounds are argolaphos, a broad-spectrum antibacterial phosphonopeptide composed of aminomethylphosphonate in peptide linkage to a rare amino acid N(5)-hydroxyarginine; valinophos, an N-acetyl l-Val ester of 2,3-dihydroxypropylphosphonate; and phosphonocystoximate, an unusual thiohydroximate-containing molecule representing a new chemotype of sulfur-containing phosphonate natural products. Analysis of the genome sequences from the remaining strains suggests that the majority of the phosphonate biosynthetic repertoire of Actinobacteria has been captured at the gene level. This dereplicated strain collection now provides a reservoir of numerous, as yet undiscovered, phosphonate natural products.

  12. General Linker Diversification Approach to Bivalent Ligand Assembly: Generation of an Array of Ligands for the Cation-Independent Mannose 6-Phosphate Receptor.

    Science.gov (United States)

    Fei, Xiang; Zavorka, Megan E; Malik, Guillaume; Connelly, Christopher M; MacDonald, Richard G; Berkowitz, David B

    2017-08-18

    A generalized strategy is presented for the rapid assembly of a set of bivalent ligands with a variety of linking functionalities from a common monomer. Herein, an array of phosphatase-inert mannose-6-phosphonate-presenting ligands for the cation-independent-mannose 6-phosphate receptor (CI-MPR) is constructed. Receptor binding affinity varies with linking functionality-the simple amide and 1,5-triazole(tetrazole) being preferred over the 1,4-triazole. This approach is expected to find application across chemical biology, particularly in glycoscience, wherein multivalency often governs molecular recognition.

  13. Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

    KAUST Repository

    Paniagua, Sergio A.

    2016-05-26

    Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

  14. Sorption of Perfluoroalkyl Phosphonates and Perfluoroalkyl Phosphinates in Soils.

    Science.gov (United States)

    Lee, Holly; Mabury, Scott Andrew

    2017-02-22

    Perfluoroalkyl phosphonates (PFPAs) and perfluoroalkyl phosphinates (PFPiAs) are recently discovered perfluoroalkyl acids (PFAAs) that have been widely detected in house dust, aquatic biota, surface water, and wastewater environments. The sorption of C6, C8, and C10 monoalkylated PFPAs and C6/C6, C6/C8, and C8/C8 dialkylated PFPiAs was investigated in seven soils of varying geochemical parameters. Mean distribution coefficients, logKd*, ranged from 0.2 to 2.1 for the PFPAs and PFPiAs and were generally observed to increase with perfluoroalkyl chain length. The logKd* of PFPiAs calculated here (1.6-2.1) were similar to those previously measured for the longer-chain perfluorodecane sulfonate (1.9, PFDS) and perfluoroundecanoate (1.7, PFUnA) in sediments, but overall when compared as a class, were greater than those for the perfluoroalkane sulfonates (-0.8-1.9, PFSAs), perfluoroalkyl carboxylates (-0.4-1.7, PFCAs), and PFPAs (0.2-1.5). No single soil-specific parameter, such as pH and organic carbon content, was observed to control the sorption of PFPAs and PFPiAs, the lack of which may be attributed to competing interferences in the naturally heterogeneous soils. The PFPAs were observed to desorb to a greater extent and likely circulate as aqueous contaminants in the environment, while the more sorptive PFPiAs would be preferentially retained by environmental solid phases.

  15. Adsorption of Macroporous Phosphonic Acid Resin for Nickel

    Institute of Scientific and Technical Information of China (English)

    XIONG Chunhua; YAO Caiping; LI Jianrong

    2005-01-01

    The adsorption behavior and mechanism of a novel chelate resin, macroporous phosphonic acid resin ( PAR ) for Ni ( Ⅱ ) were investigated. The statically saturated adsorption capacity is 64.3 mg · g - 1 resin at 298 K in HAc-NaAc medium. The Ni( Ⅱ ) adsorbed on PAR can be elated by 0.5mol· L-1 HCl and the elution percentage reaches 96.6% . The resin can be regenerated and reused without obvious decrease in adsorption capacity. The apparent adsorption rate coastant is k298 = 2.6 × 10-5 s -1 . The adsorption behavior of PAR for Ni ( Ⅱ ) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △ H, free en ergy change △ G and entropy change △ S of PAR for Ni ( Ⅱ ) are 3. 36 kJ· mol-1 , - 5.47 kJ· mol - 1 and 29.6J·mol-1 · K- 1, respectively. The apparent activation energy is Ea =12 . 2 kJ · mol-1 The molar coordination ratio of the functional group of PAR to Ni( Ⅱ ) is about 4: 1. The adsorption mechanism of PAR for Ni( Ⅱ ) was examined by a chemical method and IR spectrometry.

  16. 三苯基锗炔基膦酸酯的合成和表征(英文)%Synthesis and Characterization of Triphenylgermanium Alkynyl Phosphonates

    Institute of Scientific and Technical Information of China (English)

    尹汉东; 朱德中; 王勇; 马春林

    2002-01-01

    Twelve triphenylgermanium alkynyl phosphonates were synthesized by the reaction of triphenylgermanium chloride with corresponding alkynyl phosphates. Their structures were characterized by elemental analysis, IR,1H NMR and MS. The results showed that O-bis (triphenylgermanium) alkynyl phosphonates contain both four-and five-coordinated germanium atom and that O-triphenylgermanium alkynyl phosphonates contain five-coordinated germanium atom.``

  17. Structural investigation of the zirconium-titanium based amino trimethylene phosphonate hybrid coating on aluminum alloy

    Institute of Scientific and Technical Information of China (English)

    Shuanghong WANG; Changsheng LIU; Fengjun SHAN

    2009-01-01

    A zirconium-titanium based amino trimethylene phosphonate hybrid coating on AA6061 aluminum alloys was formed by dipping in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid (ATMP) solution for improving the lacquer adhesion and corrosion resistance as a substitute of chromate coatings. The morphol-ogy and structure of the hybrid coating were studied by means of scanning electror microscopy (SEM) and atomic force microscopy (AFM). The surface compositior and structure characteristics were also investigated by means of X-ray photoelectron spectroscopy (XPS) and Fourier transformation infra-red spectroscopy (FTIR). The results of SEM and AFM show that the hybrid coating present piece particle distrib-ution which is much denser than that of the zirconium-titanium coating. The results of XPS and FTIR indicate that the hybrid coating is a hybrid composite structure composed of both the zirconium-titanium and amino trimethylene phosphonate coat-ings.

  18. Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection.

    Science.gov (United States)

    Yang, Weiting; Tian, Hong-Rui; Li, Jian-Ping; Hui, Yuan-Feng; He, Xiang; Li, Jiyang; Dang, Song; Xie, Zhigang; Sun, Zhong-Ming

    2016-10-17

    Rational selection and modification of rare earth metal centers and photoactive organic linkers enables designable multiphotofunctionality to come to fruition in new hybrid coordination polymer materials. By using a viologen-functionalized diphosphonate linker, two terbium phosphonate compounds (Tb-1 and Tb-2) have been constructed, which display reversible photochromic reactions in response to UV light and soft X-ray irradiation. In addition, the photo-induced electron-transfer reaction can modulate the luminescent emission to thus realize photoluminescence switching behavior. Furthermore, both terbium phosphonates can serve as highly sensitive sensors to probe Cu(2+) in solution through their luminescence. Thus, they represent the first photochromic examples of lanthanide phosphonate-based materials with photomodulated luminescence and sensitive detection of metal ions.

  19. Synthesis, Bonding, and Reactivity of Vanadium(IV) Oxido-Fluorido Compounds with Neutral Chelate Ligands of the General Formula cis-[V(IV)(═O)(F)(L(N-N))2](+).

    Science.gov (United States)

    Passadis, Stamatis S; Tsiafoulis, Constantinos; Drouza, Chryssoula; Tsipis, Athanassios C; Miras, Haralampos N; Keramidas, Anastasios D; Kabanos, Themistoklis A

    2016-02-15

    Reaction of the oxidovanadium(IV)-L(N-N) species (L(N-N) is bipy = 2,2'-bipyridine or bipy-like molecules) with either BF4(-) or HF and/or KF results in the formation of compounds of the general formula cis-[V(IV)(═O)(F)(L(N-N))2](+). Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the V(IV)-F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.

  20. [Application of phosphates and phosphonates prodrugs in drug research and development].

    Science.gov (United States)

    Ji, Xun; Wang, Jiang; Zhang, Lei; Zhao, Lin-Xiang; Jiang, Hua-Liang; Liu, Hong

    2013-05-01

    Based on the character of the molecular structure, the prodrugs of phosphates and phosphonates were divided into two categories. The first is the drug which contained the phosphate group, introducing protected groups to increase lipophilicity and improve bioavailability. The other one is the drug which had no phosphate group, introducing the phosphate group into molecules to enhance the solubility, regulate the distribution coefficient and enhance the drug-like property. This review focuses on the application of phosphates and phosphonates in drug research and development based on improvement of physico-chemical property, drug safety and the pharmacokinetics.

  1. Yield Improvement and Energy Savings Uing Phosphonates as Additives in Kraft pulping

    Energy Technology Data Exchange (ETDEWEB)

    Ulrike W. Tschirner; Timothy Smith

    2007-03-31

    Project Objective: Develop a commercially viable modification to the Kraft process resulting in energy savings, increased yield and improved bleachability. Evaluate the feasibility of this technology across a spectrum of wood species used in North America. Develop detailed fundamental understanding of the mechanism by which phosphonates improve KAPPA number and yield. Evaluate the North American market potential for the use of phosphonates in the Kraft pulping process. Examine determinants of customer perceived value and explore organizational and operational factors influencing attitudes and behaviors. Provide an economic feasibility assessment for the supply chain, both suppliers (chemical supply companies) and buyers (Kraft mills). Provide background to most effectively transfer this new technology to commercial mills.

  2. Surface modification of alumina-coated silica nanoparticles in aqueous sols with phosphonic acids and impact on nanoparticle interactions.

    Science.gov (United States)

    Pauly, Céline Schmitt; Genix, Anne-Caroline; Alauzun, Johan G; Sztucki, Michael; Oberdisse, Julian; Hubert Mutin, P

    2015-07-15

    It is often necessary to tailor nanoparticle (NP) interactions and their compatibility with a polymer matrix by grafting organic groups, but the commonly used silanization route offers little versatility, particularly in water. Herein, alumina-coated silica NPs in aqueous sols have been modified for the first time with low molecular-weight phosphonic acids (PAs) bearing organic groups of various hydrophobicities and charges: propyl, pentyl and octyl PAs, and two PAs bearing hydrophilic groups, either a neutral diethylene glycol (DEPA) or a potentially charged carboxylic acid (CAPA) group. The interactions and aggregation in the sols have been investigated using zeta potential measurements, dynamic light scattering, transmission electron microscopy, and small-angle scattering methods. The surface modification has been studied using FTIR and (31)P MAS NMR spectroscopies. Both high grafting density ρ and high hydrophobicity of the groups on the PAs induced aggregation, whereas suspensions of NPs grafted by DEPA remained stable up to the highest ρ. Unexpectedly, CAPA-modified NPs showed aggregation even at low ρ, suggesting that the carboxylic end group was also grafted to the surface. Surface modification of aqueous sols with PAs allows thus for the grafting of a higher density and a wider variety of organic groups than organosilanes, offering an increased control of the interactions between NPs, which is of interest for designing waterborne nanocomposites.

  3. Correlation of normal boiling points of dialkylalkyl phosphonates with topological indices on the gas chromatographic retention data

    Energy Technology Data Exchange (ETDEWEB)

    Panneerselvam, K., E-mail: kpselvam@igcar.gov.in; Rao, C.V.S. Brahmmananda; Antony, M.P.

    2015-01-20

    Highlights: • Normal boiling points of dialkylalkyl phosphonates measured by using GC technique. • Retention times have been determined by using temperature programmed technique. • Topological indices derived to encode the structural aspects of phosphonates. • QSPR discipline have been developed for predicting normal boiling points. • Statistical characteristics were used for validity of the QSPR discipline. - Abstract: The normal boiling point of twelve dialkylalkyl phosphonates has been determined using gas chromatographic technique. Dibutylhydrogen phosphonate has been used as reference for computing normal boiling point of dialkylalkyl phosphonates. Retention times of dialkylalkyl phosphonates have been measured by using temperature programmed technique. The topological indices namely, odd–even index, atom type index and steric effect index have been designed to capture surface interaction parameters. It was found to exhibit excellent correlation of the topological indices to the normal boiling point of dialkylalkyl phosphonates. Multiple linear regression analysis has been performed for development of quantitative structure property relationships discipline. It exhibited good predictive power (R{sup 2} = 0.998)

  4. Deprotonation of C-alkyl groups of cationic N-heterocyclic ligands.

    Science.gov (United States)

    Cabeza, Javier A; García-Álvarez, Pablo; Pérez-Carreño, Enrique; Pruneda, Vanessa

    2012-04-21

    The C-alkyl groups of C-alkylpyrazinium-derived ligands have been selectively deprotonated by K[N(SiMe(3))(2)], through charge-controlled processes, to give neutral products that contain C-alkylidenepyrazine-derived ligands.

  5. Enantioselective addition of diphenyl phosphonate to ketimines derived from isatins catalyzed by binaphthyl-modified organocatalysts

    Science.gov (United States)

    Jang, Hee Seung; Kim, Yubin

    2016-01-01

    Summary Chiral binaphthyl-modified squaramide-catalyzed enantioselective addition of diphenyl phosphonate to ketimines derived from isatins has been achieved. This method affords practical and efficient access to chiral 3-amino-3-phosphonyl-substituted oxindole derivatives in high yields with excellent enantioselectivities (up to 99% ee). PMID:27559405

  6. 40 CFR 721.6075 - Phosphonic acid, 1,1-methylenebis-tetrakis(1-methylethyl) ester.

    Science.gov (United States)

    2010-07-01

    ...-tetrakis(1-methylethyl) ester. 721.6075 Section 721.6075 Protection of Environment ENVIRONMENTAL PROTECTION...-methylethyl) ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as phosphonic acid, 1,1-methylenebis-tetrakis(1-methylethyl) ester (PMN P-95-168)...

  7. Enantioselective addition of diphenyl phosphonate to ketimines derived from isatins catalyzed by binaphthyl-modified organocatalysts

    Directory of Open Access Journals (Sweden)

    Hee Seung Jang

    2016-07-01

    Full Text Available Chiral binaphthyl-modified squaramide-catalyzed enantioselective addition of diphenyl phosphonate to ketimines derived from isatins has been achieved. This method affords practical and efficient access to chiral 3-amino-3-phosphonyl-substituted oxindole derivatives in high yields with excellent enantioselectivities (up to 99% ee.

  8. Antiviral effect of ribavirin and acyclic nucleosid phosphonates against Radish mosaic virus

    OpenAIRE

    VOZÁBOVÁ, Tereza

    2010-01-01

    Evaluation of the antiviral effectiveness of ribavirin and acyclic nucleotide phosphonates to radish mosaic virus. Virus inoculation of plants with RaMV and immunological assay of the virus by ELISA. Subsequent application of antiviral agents and monitoring relative content of the virus in plants. Subsequent processing of data in tables and graphs, and then statistical evaluation.

  9. Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

    Science.gov (United States)

    Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator to the dia...

  10. Metal phosphonate hybrid mesostructures: environmentally friendly multifunctional materials for clean energy and other applications.

    Science.gov (United States)

    Ma, Tian-Yi; Yuan, Zhong-Yong

    2011-10-17

    The synthesis of porous hybrid materials has been extended to mesoporous non-silica-based organic-inorganic hybrid materials, in which mesoporous metal phosphonates represent an important family. By using organically bridged polyphosphonic acids as coupling molecules, the homogeneous incorporation of a considerable number of organic functional groups into the metal phosphonate hybrid framework has been realized. Small amounts of organic additives and the pH value of the reaction solution have a large impact on the morphology and textural properties of the resultant hybrid mesoporous metal phosphonate solids. Cationic and nonionic surfactants can be used as templates for the synthesis of ordered mesoporous metal phosphonates. The materials are used as efficient adsorbents for heavy metal ions, CO₂, and aldehydes, as well as in the separation of polycyclic aromatic hydrocarbons. They are also useful photocatalysts under UV and simulated solar light irradiation for organic dye degradation. Further functionalization of the synthesized mesoporous hybrids makes them oxidation and acid catalysts, both with impressive performances in the fields of sustainable energy and environment. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  12. Fluorescent carboxylic and phosphonic acids: comparative photophysics from solution to organic nanoparticles.

    Science.gov (United States)

    Faucon, Adrien; Lenk, Romaric; Hémez, Julie; Gautron, Eric; Jacquemin, Denis; Le Questel, Jean-Yves; Graton, Jérôme; Brosseau, Arnaud; Ishow, Eléna

    2013-08-14

    Phosphonic and carboxylic fluorescent nanoparticles have been fabricated by direct reprecipitation in water. Their fluorescence properties strongly differ from those of the corresponding esters where strong H-bonding formation is prohibited. Comparative experiments between the two acid derivatives, differing only in their acid functions while keeping the same alkyl chain, have evidenced the peculiar behavior of the phosphonic acid derivative compared to its carboxylic analog. A dramatic emission quenching for the phosphonic acid in aprotic toluene could be observed while a fivefold increase in the fluorescence signal was observed for molecules assembled as nanoparticles. Such properties have been attributed on the theoretical basis to the formation of folded conformers in solution, leading to deactivation of the radiative excited state through intramolecular H-bonding. These studies evidence for the first time through time-resolved fluorescence measurements the stronger H-donating character of phosphonic acids compared to the carboxylic ones, and provide information on the degree of structural heterogeneity within the nanoparticles. They should pave the way for the rational fabrication of chelating acid fluorophores, able to complex metal oxides to yield stiff hybrid magnetofluorescent nanoparticles which are attracting considerable attention in the growing fields of bimodal imaging and vectorization applications.

  13. Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant

    Science.gov (United States)

    There has been a great scientific interest in exploring the great potential of the piperazine-phosphonates in flame retardant (FR) application on cotton fabric by investigating the thermal decomposition of cotton fabric treated with them. This research tries to understand the mode of action of the t...

  14. Seasonal expression of the picocyanobacterial phosphonate transporter gene phnD in the Sargasso Sea

    Directory of Open Access Journals (Sweden)

    Irina N Ilikchyan

    2010-12-01

    Full Text Available In phosphorus-limited marine environments, picocyanobacteria (Synechococcus and Prochlorococcus spp. can hydrolyze naturally occurring phosphonates as a P source. Utilization of 2-aminoethylphosphonate (2-AEP is dependent on expression of the phn genes, encoding functions required for uptake and C-P bond cleavage. Prior work has indicated that expression of picocyanobacterial phnD, encoding the phosphonate binding protein of the phosphonate ABC transporter, is a proxy for the assimilation of phosphonates in natural assemblages of Synechococcus spp. and Prochlorococcus spp (Ilikchyan et al. 2009. In this study, we expand this work to assess seasonal phnD expression in the Sargasso Sea. By RT-PCR, our data confirm that phnD expression is constitutive for the Prochlorococcus spp. detected, but in Synechococcus spp., phnD transcription follows patterns of phosphorus availability in the mixed layer. Specifically, our data suggest that phnD is repressed in the spring when P is bioavailable following deep winter mixing. In the fall, phnD expression follows a depth dependent pattern reflecting depleted P at the surface following summertime drawdown, and elevated P at depth.

  15. Adsorption of Phosphonate Antiscalant from Reverse Osmosis Membrane Concentrate onto Granular Ferric Hydroxide

    NARCIS (Netherlands)

    Boels, L.; Keesman, K.J.; Witkamp, G.J.

    2012-01-01

    Adsorptive removal of antiscalants offers a promising way to improve current reverse osmosis (RO) concentrate treatment processes and enables the reuse of the antiscalant in the RO desalination process. This work investigates the adsorption and desorption of the phosphonate antiscalant nitrilotris(m

  16. Olefin cross-metathesis for the synthesis of alkenyl acyclonucleoside phosphonates.

    Science.gov (United States)

    Bessières, Maxime; De Schutter, Coralie; Roy, Vincent; Agofoglio, Luigi A

    2014-12-12

    The detailed synthetic protocol for the straightforward, efficient synthesis of various alkenyl acyclonucleosides, including challenging trisubstituted alkenyl acyclonucleoside phosphonates, is described. The key step of those syntheses is an olefin cross-metathesis reaction between two olefins selected based on their reactivity using well-defined ruthenium alkylidene catalysts.

  17. A diethyl phosphonate containing oxazoline: Synthesis and characterization of monomer and homopolymer

    Energy Technology Data Exchange (ETDEWEB)

    Hermes, R.E.; Thompson, R.D.; Valdez, L.S.

    1995-05-01

    A diethyl phosphonate oxazoline monomer and its polymer have been synthesized. The monomer appears to polymerize via a ring-opening mechanism giving the expected polyethyleneimine backbone with pendant carbonyl groups. Two distinct molecular weights were produced during polymerization suggesting two mechanisms of chain growth. Studies are underway to elucidate the reasons for this. This polymer has potential as a metal-chelating agent.

  18. Functionalization of SBA-15 mesoporous silica by Cu-phosphonate units: Probing of synthesis route

    Energy Technology Data Exchange (ETDEWEB)

    Laskowski, Lukasz, E-mail: lukasz.laskowski@kik.pcz.pl [Czestochowa University of Technology, Institute of Computational Intelligence, Al. Armii Krajowej 36, 42-201 Czestochowa (Poland); Czestochowa University of Technology, Institute of Physics, Al. Armii Krajowej 19, 42-201 Czestochowa (Poland); Laskowska, Magdalena, E-mail: magdalena.laskowska@onet.pl [Czestochowa University of Technology, Institute of Physics, Al. Armii Krajowej 19, 42-201 Czestochowa (Poland)

    2014-12-15

    Mesoporous silica SBA-15 containing propyl-copper phosphonate units was investigated. The structure of mesoporous samples was tested by N{sub 2} isothermal sorption (BET and BHJ analysis), TEM microscopy and X-Ray scattering. Quantitative analysis EDX has given information about proportions between component atoms in the sample. Quantitative elemental analysis has been carried out to support EDX. To examine bounding between copper atoms and phosphonic units the Raman spectroscopy was carried out. As a support of Raman scattering, the theoretical calculations were made based on density functional theory, with the B3LYP method. By comparison of the calculated vibrational spectra of the molecule with experimental results, distribution of the active units inside silica matrix has been determined. - Graphical abstract: The present study is devoted to mesoporous silica SBA-15 containing propyl-copper phosphonate units. The species were investigated to confirm of synthesis procedure correctness by the micro-Raman technique combined with DFT numerical simulations. Complementary research was carried out to test the structure of mesoporous samples. - Highlights: • SBA-15 silica functionalized with propyl-copper phosphonate units was synthesized. • Synthesis efficiency probed by Raman study supported with DFT simulations. • Homogenous distribution of active units was proved. • Synthesis route enables precise control of distance between copper ions.

  19. Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

    Science.gov (United States)

    Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO), and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl, and n-butyl, using radical initiator. A staged addition of the lipid and the initiator was needed...

  20. A comparative study of proton transport properties of zirconium (IV) phosphonates

    Indian Academy of Sciences (India)

    Heemanshu Patel; Uma Chudasama

    2006-12-01

    Novel amorphous zirconium (IV) phosphonates of the class of tetravalent metal acid (TMA) salts have been synthesized by sol–gel method where phosphonates used are hydroxy ethylidene diphosphonic acid (HEDP), amino tri(methylene phosphonic acid) (ATMP) and diethylenetriamine penta(methylenephosphonic acid) (DETPMP) to give ZrHEDP, ZrATMP and ZrDETPMP, respectively. These materials have been characterized for elemental analysis, Zr and P (ICP-AES) and carbon, hydrogen, nitrogen contents (CHN analyser), thermal analysis (TGA, DSC), X-ray analysis and FTIR spectroscopy. Chemical resistivity of these materials has been accessed in acids, bases and organic solvent media. The protons present in the structural hydroxyl groups indicate good potential for TMA salts to exhibit solid state proton conduction. The transport properties of these materials has been explored by measuring specific proton conductance at different temperatures in the range 30–120°C at 10°C intervals, using SOLARTRON DATASET impedance analyser (SI 1260) over a frequency range 1 Hz–10 MHz at a signal level below 1 V. Based on the specific conduction data and Arrhenius plots, a suitable mechanism has been proposed and conductance performance of zirconium phosphonates compared with zirconium phosphate (ZrP).

  1. What is Neutrality?

    NARCIS (Netherlands)

    Pierik, R.; van der Burg, W.

    2014-01-01

    This paper reinvestigates the question of liberal neutrality. We contend that current liberal discussions have been dominated - if not hijacked - by one particular interpretation of what neutrality could imply, namely, exclusive neutrality, that aims to exclude religious and cultural expressions

  2. Crystal structure of a compact three-dimensional metal–organic framework based on Cs+ and (4,5-dicyano-1,2-phenylenebis(phosphonic acid

    Directory of Open Access Journals (Sweden)

    Ricardo F. Mendes

    2016-12-01

    Full Text Available A new metal–organic framework compound, poly[[μ7-dihydrogen (4,5-dicyano-1,2-phenylenediphosphonato](oxoniumcaesium], [Cs(C8H4N2O6P2(H3O]n (I, based on Cs+ and the organic linker 4,5-dicyano-1,2-phenylenebis(phosphonic acid, (H4cpp, containing two distinct coordinating functional groups, has been prepared by a simple diffusion method and its crystal structure is reported. The coordination polymeric structure is based on a CsO8N2 complex unit comprising a monodentate hydronium cation, seven O-atom donors from two phosphonium groups of the (H2cpp2− ligand, and two N-atom donors from bridging cyano groups. The high level of connectivity from both the metal cation and the organic linker allow the formation of a compact and dense three-dimensional network without any crystallization solvent. Topologically (I is a seven-connected uninodal network with an overall Schäfli symbol of {417.64}. Metal cations form an undulating inorganic layer, which is linked by strong and highly directional O—H...O hydrogen-bonding interactions. These metallic layers are, in turn, connected by the organic ligands along the [010] direction to form the overall three-dimensional framework structure.

  3. Synthesis and characterization of calcium hydroxy and fluoroapatite functionalized with methyl phosphonic dichloride

    Energy Technology Data Exchange (ETDEWEB)

    Agougui, Hassen; Aissa, Abdallah [Laboratoire de Physico-Chimie des Materiaux, Faculte des Sciences de Monastir, 5019 Monastir (Tunisia); Debbabi, Mongi, E-mail: m.debbabi@yahoo.fr [Laboratoire de Physico-Chimie des Materiaux, Faculte des Sciences de Monastir, 5019 Monastir (Tunisia)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Surface reactivity of apatites toward methyl phosphonic dichloride is tested. Black-Right-Pointing-Pointer Chemical analysis shows that hydroxyapatite is more reactive. Black-Right-Pointing-Pointer NMR spectra show the formation of Ca-O-P{sub org} and P{sub inorg}-O-P{sub org} bonds. Black-Right-Pointing-Pointer AFM indicated that the texture surface was changed by grafting. - Abstract: The nature of apatite-organic molecule interaction was the subject of many investigations. Grafting the organic molecule onto the inorganic support may precede through either formation of covalent bonds or ionic interaction between superficial hydroxyl on the apatite surface and organic functions. The hybrid materials obtained by functionalization of apatite surfaces with phosphonate moieties are of interest for their potential applications such in catalysis, chromatography and biomedical domain. In this scope, calcium hydroxyl and fluoroapatite (CaHAp and CaFAp) were prepared in the presence of the methyl phosphonic dichloride (MPO), by contact method in organic solvent at 25 Degree-Sign C for 2 days. The products are rigorously characterized by chemical analysis, infrared (IR), MAS-NMR spectroscopies, powder X-ray diffraction (XRD), atomic force microscopy (AFM) and specific surface area (SSA). The X-ray powder analysis showed that the crystallinity was sensibly affected by the presence of organic moieties. The IR spectroscopy showed new vibration modes appearing related to phosphonate groups essentially at 2930, 1315, 945, 764 and 514 cm{sup -1}. The {sup 31}P MAS NMR spectrum for hydroxy and fluoroapatite exhibits a single signal at 2.8 ppm. After reaction with (MPO) the spectra show the presence of new signals, assigned to the formation of organic-inorganic bond between the superficial hydroxyl groups of the apatite ({identical_to}CaOH) and ({identical_to}POH) and methyl phosphonic dichloride. The SSA decreases with increasing

  4. Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

    Science.gov (United States)

    Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

    2015-11-15

    Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore.

  5. Synthesis and characterization of tin(IV) phenyl phosphonate in nano form

    Indian Academy of Sciences (India)

    Chitra Sumej; Beena Raveendran

    2008-08-01

    An inorgano–organic ion exchanger, Sn(IV) phenyl phosphonate, has been synthesized in amorphous form. Further, an attempt has been made to synthesize Sn(IV) phenyl phosphonate in the nano form. The materials have been characterized for elemental analysis (ICP–AES), thermal analysis (TGA), X-ray analysis and FTIR spectroscopy. Chemical resistivity of these materials has been accessed in acidic, basic and organic solvent media. Catalytic activity has been studied and compared by using esterification of ethylene glycol as a model reaction wherein glycoldiacetate has been prepared. The transport properties of these materials have been explored by measuring specific proton conduction at different temperatures using SOLARTRON DATASET impedance analyser over a frequency range 1 Hz–1 MHz. It has been observed that Sn(IV) phenyl phosphate in the nano form behaves as a better Bronsted catalyst and proton conductor as compared to the amorphous form.

  6. Synergistic extraction of praseodymium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qian; WU Dong-bei; BAO Bo-rong

    2009-01-01

    The synergistic extraction of Pr3+ from hydrochloric medium using mixture of 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507, HL) and 8-Hydroxyquinoline (HQ) in heptane was investigated. The effect of equilibrium of aqueous acidity on extraction of Pr3+ was discussed. The effect of extractant concentraction, different diluents, equilibrium time and acetate ion concentration on extraction reaction were also studied. With a method of double-logarithmic slope, composition of the extracted species on 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinolinc was derived. The result shows that the synergistic extraction system not only overcomes emulsification of 8-Hydroxyquinoline, but also shows perfect capacity of synergistic extraction. The largest synergistic enhancement factor can be calculated to be 5.49 at pH 3.6 for Pr3+.

  7. Functionalization of SBA-15 mesoporous silica by Cu-phosphonate units: Probing of synthesis route

    Science.gov (United States)

    Laskowski, Lukasz; Laskowska, Magdalena

    2014-12-01

    Mesoporous silica SBA-15 containing propyl-copper phosphonate units was investigated. The structure of mesoporous samples was tested by N2 isothermal sorption (BET and BHJ analysis), TEM microscopy and X-Ray scattering. Quantitative analysis EDX has given information about proportions between component atoms in the sample. Quantitative elemental analysis has been carried out to support EDX. To examine bounding between copper atoms and phosphonic units the Raman spectroscopy was carried out. As a support of Raman scattering, the theoretical calculations were made based on density functional theory, with the B3LYP method. By comparison of the calculated vibrational spectra of the molecule with experimental results, distribution of the active units inside silica matrix has been determined.

  8. Synthesis and Antiviral Bioactivity of Chiral Thioureas Containing Leucine and Phosphonate Moieties

    Directory of Open Access Journals (Sweden)

    Jian Wu

    2010-07-01

    Full Text Available A series of novel chiral thioureas 3a-n bearing leucine and phosphonate moieties were synthesized in excellent yields. The structures of the compounds were completely characterized by elemental analysis, IR, 1H-, 13C-, 31P- and 19F-NMR spectral data. A half-leaf method was used to determine the in vivo protective and curative efficacies of the title products against tobacco mosaic virus (TMV. The compounds 3l and 3n displayed good in vivo protection and curative effects against TMV with inhibitory rates of 60.1, 62.8% (protection and 56.7, 53.6% (curative at 0.5 mg/mL, respectively. To the best of our knowledge, this is the first report on the antiviral activity of chiral thioureas containing leucine and phosphonate moieties.

  9. Low adhesion, non-wetting phosphonate self-assembled monolayer films formed on copper oxide surfaces.

    Science.gov (United States)

    Hoque, E; DeRose, J A; Bhushan, B; Hipps, K W

    2009-07-01

    Self-assembled monolayer (SAM) films have been formed on oxidized copper (Cu) substrates by reaction with 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octadecylphosphonic acid (ODP), decylphosphonic acid (DP), and octylphosphonic acid (OP) and then investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurement (CAM), and atomic force microscopy (AFM). The presence of alkyl phosphonate molecules, PFDP, ODP, DP, and OP, on Cu were confirmed by CAM and XPS analysis. No alkyl phosphonate molecules were seen by XPS on unmodified Cu as a control. The PFDP/Cu and ODP/Cu SAMs were found to be very hydrophobic having water sessile drop static contact angles of more than 140 degrees , while DP/Cu and OP/Cu have contact angles of 119 degrees and 76 degrees , respectively. PFDP/Cu, ODP/Cu, DP/Cu, and OP/Cu SAMs were studied by friction force microscopy, a derivative of AFM, to better understand their micro/nanotribological properties. PFDP/Cu, ODP/Cu, and DP/Cu had comparable adhesive force, which is much lower than that for unmodified Cu. ODP/Cu had the lowest friction coefficient followed by PFDP/Cu, DP/Cu, and OP/Cu while unmodified Cu had the highest. XPS data gives some indication that a bidentate bond forms between the alkyl phosphonate molecules and the oxidized Cu surface. Hydrophobic phosphonate SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for anti-wetting, low adhesion surfaces.

  10. Synthesis of 0,0-diethyl-α-(p-toluenesulphonamido) phosphonates by Mannich-type reaction

    Institute of Scientific and Technical Information of China (English)

    陈茹玉; 戴庆; 张殿坤; 杨秀凤

    1995-01-01

    A series of O,O-diethyl-α-(p-toluenesulphonamido)phosphonates have been synthesized by theMannich-type reaction of p-toluenesulphonamide,substituted benzaldehydes and diethyl phosphite with acetylchloride as the solvent.The mechanism of the reaction is suggested,and the structures of new products areconfirmed by 1H NMR,31p NMR,elemental analysis and X-ray diffraction.The results of preliminarybioassay showed that some of them possess herbicidal activities.

  11. In situ chemical functionalization of gallium nitride with phosphonic acid derivatives during etching.

    Science.gov (United States)

    Wilkins, Stewart J; Greenough, Michelle; Arellano, Consuelo; Paskova, Tania; Ivanisevic, Albena

    2014-03-04

    In situ functionalization of polar (c plane) and nonpolar (a plane) gallium nitride (GaN) was performed by adding (3-bromopropyl) phosphonic acid or propyl phosphonic acid to a phosphoric acid etch. The target was to modulate the emission properties and oxide formation of GaN, which was explored through surface characterization with atomic force microscopy, X-ray photoelectron spectroscopy, photoluminescence (PL), inductively coupled plasma-mass spectrometry, and water contact angle. The use of (3-bromopropyl) phosphonic acid and propyl phosphonic acid in phosphoric acid demonstrated lower amounts of gallium oxide formation and greater hydrophobicity for both sample sets, while also improving PL emission of polar GaN samples. In addition to crystal orientation, growth-related factors such as defect density in bulk GaN versus thin GaN films residing on sapphire substrates were investigated as well as their responses to in situ functionalization. Thin nonpolar GaN layers were the most sensitive to etching treatments due in part to higher defect densities (stacking faults and threading dislocations), which accounts for large surface depressions. High-quality GaN (both free-standing bulk polar and bulk nonpolar) demonstrated increased sensitivity to oxide formation. Room-temperature PL stands out as an excellent technique to identify nonradiative recombination as observed in the spectra of heteroepitaxially grown GaN samples. The chemical methods applied to tune optical and physical properties of GaN provide a quantitative framework for future novel chemical and biochemical sensor development.

  12. Photocatalytic behavior of phosphonate-based hybrid materials on dyes and phenols degradation

    OpenAIRE

    Bazaga-García, Montse; Colodrero, Rosario M.P.; Olivera-Pastor, Pascual; SANTACRUZ, ISABEL; Aranda, Miguel A. G.

    2013-01-01

    There is increasing interest in using heterogeneous catalysis for mineralization of organic pollutants. Within Advanced Oxidation Processes (AOPs), Photo-Fenton reaction is one of the most efficient methodologies. To date, most of heterogeneous iron catalysts studied was based on oxides or hydroxides. We extend here our previous studies on phenol photodegradation [1] by exploring the photocatalytic activity of various hybrid MII phosphonates (MII = Mn, Fe, Cu) for several organ...

  13. Polysulfone Functionalized With Phosphonated Poly(pentafluorostyrene) Grafts for Potential Fuel Cell Applications

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja

    2012-01-01

    A multi‐step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne‐end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting....... The proposed synthetic route opens the possibility to tune copolymers’ hydrophilic–hydrophobic balance to obtain membranes with an optimal balance between proton conductivity and mechanical properties....

  14. Efficient modification of metal oxide surfaces with phosphonic acids by spray coating.

    Science.gov (United States)

    Bulusu, Anuradha; Paniagua, Sergio A; MacLeod, Bradley A; Sigdel, Ajaya K; Berry, Joseph J; Olson, Dana C; Marder, Seth R; Graham, Samuel

    2013-03-26

    We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time. The data show that the work function shifts and surface coverage by the phosphonic acid were similar to or greater than those obtained by the dip-coating method. When the deposition temperature was increased, the magnitude of the surface coverage and work function shift was also found to increase. The rapid exposure of the spray coating was found to result in less etching of zinc-containing oxides than the dip-coating method. Bulk heterojunction solar cells made of polyhexylthiophene (P3HT) and bis-indene-C60 (ICBA) were tested with PFBPA dip and spray-modified ITO substrates as well as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-modified ITO. The spray-modified ITO solar cells showed a similar open circuit voltage (VOC) and fill factor (FF) and a less than 5% lower short circuit current density (JSC) and power conversion efficiency (PCE) than the dip- and PEDOT:PSS-modified ITO. These results demonstrate a potential path to a scalable method to deposit phosphonic acid surface modifiers on metal oxides while overcoming the limitations of other techniques that require long exposure and post-processing times.

  15. Understanding the Mechanism of Action of Triazine-Phosphonate Derivatives as Flame Retardants for Cotton Fabric

    Directory of Open Access Journals (Sweden)

    Monique M. Nguyen

    2015-06-01

    Full Text Available Countless hours of research and studies on triazine, phosphonate, and their combination have provided insightful information into their flame retardant properties on polymeric systems. However, a limited number of studies shed light on the mechanism of flame retardancy of their combination on cotton fabrics. The purpose of this research is to gain an understanding of the thermal degradation process of two triazine-phosphonate derivatives on cotton fabric. The investigation included the preparation of diethyl 4,6-dichloro-1,3,5-triazin-2-ylphosphonate (TPN1 and dimethyl (4,6-dichloro-1,3,5-triazin-2-yloxy methyl phosphonate (TPN3, their application on fabric materials, and the studies of their thermal degradation mechanism. The studies examined chemical components in both solid and gas phases by using attenuated total reflection infrared (ATR-IR spectroscopy, thermogravimetric analysis coupled with Fourier transform infrared (TGA-FTIR spectroscopy, and 31P solid state nuclear magnetic resonance (31P solid state NMR, in addition to the computational studies of bond dissociation energy (BDE. Despite a few differences in their decomposition, TPN1 and TPN3 produce one common major product that is believed to help reduce the flammability of the fabric.

  16. Flower-like supramolecular self-assembly of phosphonic acid appended naphthalene diimide and melamine

    Science.gov (United States)

    Bhosale, Rajesh S.; Al Kobaisi, Mohammad; Bhosale, Sidhanath V.; Bhargava, Suresh; Bhosale, Sheshanath V.

    2015-09-01

    Diverse supramolecular assemblies ranging from nanometres to micrometers of small aromatic π-conjugated functional molecules have attracted enormous research interest in light of their applications in optoelectronics, chemosensors, nanotechnology, biotechnology and biomedicines. Here we study the mechanism of the formation of a flower-shaped supramolecular structure of phosphonic acid appended naphthalene diimide with melamine. The flower-shaped assembly formation was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM) imaging, furthermore, XRD and DLS used to determined mode of aggregation. Characteristically, phosphonic acid-substituted at imide position of NDIs possess two important properties resulting in the formation of controlled flower-like nanostructures: (i) the aromatic core of the NDI which is designed to optimize the dispersive interactions (π-π stacking and van der Waals interactions) between the cores within a construct and (ii) phosphonic acid of NDI interact with malamine through molecular recognition i.e. strong hydrogen-bonding (H-bonding). We believe such arrangements prevent crystallization and favour the directional growth of flower-like nanostructure in 3D fashion. These works demonstrate that complex self-assembly can indeed be attained through hierarchical non-covalent interactions of two components. Furthermore, flower-like structures built from molecular recognition by these molecules indicate their potential in other fields if combined with other chemical entities.

  17. SYNTHESIS, CHARACTERIZATION AND RING-OPENING POLYMERIZATION OF CYCLIC (ARYLENE PHOSPHONATE) OLIGOMERS

    Institute of Scientific and Technical Information of China (English)

    Hong-ming Zhang; Qing-zhong Guo; Tian-lu Chen

    2004-01-01

    A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylenc phosphonate) oligomers is over 85% by using hexadecyltrimethylammonium bromide as phase transfer catalyst (PTC) at 0 ℃. The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270℃ and the resulting polymer had a Mw of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

  18. Synthesis and properties of ApA analogues with shortened phosphonate internucleotide linkage.

    Science.gov (United States)

    Králíková, Sárka; Buděšínský, Miloš; Barvík, Ivan; Masojídková, Milena; Točík, Zdeněk; Rosenberg, Ivan

    2011-01-01

    A complete series of the 2 '-5 ' and 3 '-5 ' regioisomeric types of r(ApA) and 2 '-d(ApA) analogues with the α-hydroxy-phosphonate C3 '-O-P-CH(OH)-C4 ″ internucleotide linkage, isopolar but non-isosteric with the phosphodiester one, were synthesized and their hybridization properties with polyU studied. Due to the chirality on the 5 '-carbon atom of the modified internucleotide linkage bearing phosphorus and hydroxy moieties, each regioisomeric type of ApA dimer is split into epimeric pairs. To examine the role of the 5 '-hydroxyl of the α-hydroxy-phosphonate moiety during hybridization, the appropriate r(ApA) analogues with 3 '(2 ')-O-P-CH(2)-C4 ″ linkage lacking the 5 '-hydroxyl were synthesized. Nuclear magnetic resonance (NMR) spectroscopy study on the conformation of the modified sugar-phosphate backbone, along with the hybridization measurements, revealed remarkable differences in the stability of complexes with polyU, depending on the 5 '-carbon atom configuration. Potential usefulness of the α-hydroxy-phosphonate linkage in modified oligoribonucleotides is discussed.

  19. Covalent attachment of diamondoid phosphonic acid dichlorides to tungsten oxide surfaces.

    Science.gov (United States)

    Li, Fei Hua; Fabbri, Jason D; Yurchenko, Raisa I; Mileshkin, Alexander N; Hohman, J Nathan; Yan, Hao; Yuan, Hongyuan; Tran, Ich C; Willey, Trevor M; Bagge-Hansen, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Fokin, Andrey A; Schreiner, Peter R; Shen, Zhi-Xun; Melosh, Nicolas A

    2013-08-06

    Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).

  20. A layered mixed zirconium phosphate/phosphonate with exposed carboxylic and phosphonic groups: X-ray powder structure and proton conductivity properties.

    Science.gov (United States)

    Donnadio, Anna; Nocchetti, Morena; Costantino, Ferdinando; Taddei, Marco; Casciola, Mario; da Silva Lisboa, Fábio; Vivani, Riccardo

    2014-12-15

    A novel mixed zirconium phosphate/phosphonate based on glyphosine, of formula Zr2(PO4)H5(L)2·H2O [L = (O3PCH2)2NCH2COO], was synthesized in mild conditions. The compound has a layered structure that was solved ab initio from laboratory PXRD data. It crystallizes in the monoclinic C2/c space group with the following cell parameters: a = 29.925(3), b = 8.4225(5), c = 9.0985(4) Å, and β = 98.474(6)°. Phosphate groups are placed inside the sheets and connect the zirconium atoms in a tetradentate fashion, while uncoordinated carboxylate and P-OH phosphonate groups are exposed on the layer surface. Due to the presence of these acidic groups, the compound showed remarkable proton conductivity properties, which were studied in a wide range of temperature and relative humidity (RH). The conductivity is strongly dependent on RH and reaches 1 × 10(-3) S cm(-1) at 140 °C and 95% RH. At this RH, the activation energy of conduction is 0.15 eV in the temperature range 80-140 °C. The similarities of this structure with related structures already reported in the literature were also discussed.

  1. Neutral Operator and Neutral Differential Equation

    Directory of Open Access Journals (Sweden)

    Jingli Ren

    2011-01-01

    Full Text Available In this paper, we discuss the properties of the neutral operator (Ax(t=x(t−cx(t−δ(t, and by applying coincidence degree theory and fixed point index theory, we obtain sufficient conditions for the existence, multiplicity, and nonexistence of (positive periodic solutions to two kinds of second-order differential equations with the prescribed neutral operator.

  2. Mechanistic understanding of calcium-phosphonate solid dissolution and scale inhibitor return behavior in oilfield reservoir: formation of middle phase.

    Science.gov (United States)

    Zhang, Ping; Shen, Dong; Ruan, Gedeng; Kan, Amy T; Tomson, Mason B

    2016-08-03

    Phosphonates are an important class of mineral scale inhibitors used for oilfield scale control. By injecting the phosphonate into an oilfield reservoir, calcium-phosphonate precipitate will form and subsequently release the phosphonate into produced water for scale control. In this study, a systematic procedure is developed to mechanistically characterize an acidic calcium-phosphonate amorphous material that is later developed into a middle phase and eventually a crystalline phase. The phosphonate used in this study is diethylenetriamine pentakis (methylene phosphonic acid) (DTPMP). An amorphous calcium-DTPMP solid is precipitated by mixing a calcium-containing solution with a DTPMP solution. The stoichiometry of this initially formed solid can be experimentally confirmed via a static dissolution test. Following another dynamic development test, two additional Ca-DTPMP solid phases, i.e., a middle phase and a crystalline phase have been observed. Electron microscopy and X-ray diffraction were employed to characterize the morphology and crystallinity of different Ca-DTPMP solids of interest. Evidently, the dynamic brine flushing of the Ca-DTPMP solid developed the initially amorphous material into a middle phase solid with an amorphous/microcrystalline structure and eventually into a crystalline material. Furthermore, a dissolution characterization study was carried out to determine the solubility product of the middle phase solid at different conditions. The obtained mechanistic understanding of the Ca-DTPMP solid related to precipitation chemistry, dissolution behavior and phase transition is critical to elucidate oilfield DTPMP return data and more importantly, can optimize the oilfield scale squeeze design to achieve an extended squeeze lifetime.

  3. Amplification of infrared multiphoton dissociation efficiency in a quadruple ion trap using IR-active ligands.

    Science.gov (United States)

    Pikulski, Michael; Wilson, Jeffrey J; Aguilar, Apolonio; Brodbelt, Jennifer S

    2006-12-15

    A strategy for increasing the efficiency of infrared multiphoton dissociation (IRMPD) in a quadrupole ion trap (QIT) is described. IR-active ligands (IRALs) are incorporated into noncovalent complexes of the type [M2+(analyte) IRAL]+, where M is a transition metal such as copper or cobalt and IRAL is an auxiliary ligand with an IR-active phosphonate functional group. The complexes are formed via self-assembly in solution directly prior to ESI-MS analysis. We demonstrate this new IRMPD approach for the structural characterization of flavonoids. The fragment ions obtained by IRMPD are similar to those obtained by CAD and allow facile isomer differentiation of flavonoids. Fourier transform infrared absorption attenuated total reflectance (FTIR-ATR) and energy-variable CAD experiments indicate that the high IRMPD efficiencies stem from the very large IR absorptivities of the IR-active ligands.

  4. Fabricating Water Dispersible Superparamagnetic Iron Oxide Nanoparticles for Biomedical Applications through Ligand Exchange and Direct Conjugation

    Directory of Open Access Journals (Sweden)

    Tina Lam

    2016-05-01

    Full Text Available Stable superparamagnetic iron oxide nanoparticles (SPIONs, which can be easily dispersed in an aqueous medium and exhibit high magnetic relaxivities, are ideal candidates for biomedical applications including contrast agents for magnetic resonance imaging. We describe a versatile methodology to render water dispersibility to SPIONs using tetraethylene glycol (TEG-based phosphonate ligands, which are easily introduced onto SPIONs by either a ligand exchange process of surface-anchored oleic-acid (OA molecules or via direct conjugation. Both protocols confer good colloidal stability to SPIONs at different NaCl concentrations. A detailed characterization of functionalized SPIONs suggests that the ligand exchange method leads to nanoparticles with better magnetic properties but higher toxicity and cell death, than the direct conjugation methodology.

  5. Catalytic phosphonation of high performance polymers and POSS. Novel components for polymer blend and nanocomposite fuel cell membranes

    Energy Technology Data Exchange (ETDEWEB)

    Bock, T.R.

    2006-10-15

    Aim of this thesis was the preparation and evaluation of phosphonated high performance (HP) polyelectrolytes and polyhedral oligomeric silsesquioxanes (POSS) for polyelectrolyte membrane fuel cell (PEMFC) application. Brominated derivatives of the commercial high performance (HP) polymers poly(ethersulfone) (PES), poly(etheretherketone) (PEEK), poly(phenylsulfone) (PPSu), poly(sulfone) (PSU) and of octaphenyl-POSS of own production were phosphonated by Ni-catalysed Arbuzov reaction. Phosphonated PSU was cast into pure and blend films with sulfonated PEEK (s-PEEK) to investigate H+-conductivity, water uptake and film morphology. Blend films' properties were referenced to films containing unmodified blend partners. Solution-compounding of phosphonated octaphenyl-POSS and s-PEEK was used to produce novel nanocomposite films. An in-situ zirconisation method was assessed as convenient strategy for novel ionically crosslinked membranes of enhanced swelling resistance. Dibromo isocyanuric acid (DBI) and N-bromo succinimide (NBS) as brominating agents allowed polymer analogous preparation of the novel brominated PES and PEEK with precise reaction control. A random distribution of functional groups, i.e. polyelectrolytes' microstructural homogeneity was revealed as decisive factor concerning solubility of phosphonated PSU. Brominated phT8 was prepared with Br2 by a high temperature approach in tetrachloroethane (TCE). Brominated polymers were phosphonated by Ni-catalysis in non-coordinating high temperature solvents, such as diphenylether, benzophenone and diphenylsulfone without notable solvent influence. The lack of solvent - catalyst complexes and high reaction temperatures of 180-200 C led to halogen-free phosphonates with unprecedented high functionalities. Polymer analogous application of P(OSiMe3)3 offered a novel direct access to easily cleavable disilyl ester derivatives. These were obtained from PEEK and PSU in near quantitative yields at NiCl2-loads as

  6. Neutral Buoyancy Laboratory (NBL)

    Data.gov (United States)

    Federal Laboratory Consortium — The Neutral Buoyancy Laboratory (NBL) is an astronaut training facility and neutral buoyancy pool operated by NASA and located at the Sonny Carter Training Facility,...

  7. Synthesis of N-(alkoxycarbonyl or alkoxycarbonyl-methyl-alkoxyphosphonyl)-α-amino-O,O-diphenyl phosphonates and their bioactivities

    Institute of Scientific and Technical Information of China (English)

    李慧英; 陈茹玉; 任康太

    1997-01-01

    With phosphoric formic acid (PFA) and its analog,phosphonoacetic acid (PAA),as the lead compounds,α-amino phosphonates were introduced into PFA and PAA.The derivatives oi N-( alkoxycarbonyl-aikoxyphosphonyl)-α-arnino phosphonates (Ⅰ) and N-(alkoxycarbonyl-methyt-alkoxyphosphonyl)-α-amino phosphonates (Ⅱ) with the N-terminal of amino phosphonates bonding to phosphorus atom of PFA and PAA were synthesized via the reaction of the corresponding phosphonyl chloride with a-amino phosphonates in the presence of a base.The 31P NMK spectra of Ⅰ and Ⅱwere determined.It is found that the coupling constants 3Jpp with R3 being alkyl group were lower than those with R3 being (substituted) phenyl,and this result was discussed.The preliminary bioassay showed that some of the compounds Ⅰ and Ⅱhave better activities against tobacco mosaic virus (TMV).The inhibitory was higher than that of DHT (2,4-dioxyhexahydro-1,3,5-triazine).In addition,some of the compounds showed the activity against cancer cells.

  8. Reaction of Grignard Reagents with Diethyl Perfluoroacyl( 1-Cyanoethyl ) phosphonates. Synthesis of Perfluoroalkylated α, β-Unsaturated Nitriles with Predominant Z-Selectivity

    Institute of Scientific and Technical Information of China (English)

    SHEN,Yan-Chang(沈延昌); JIANG,Guo-Fang(江国防)

    2002-01-01

    Diethyl (1-cyanoethyl)phosphonate 1 was reacted with n-butyllithium in tetrahydrofuran ( THF ) at - 78 ℃ and the resulting carbanion 2 reacted with perfluoroalkanoic acid anhydride to afford perfluoroacylated phosphonate 3. Without isolation 3was attacked by Grognard reagents giving perfluoroalkylated α,β-unsaturated nitries in 46%-88% yields with high Zstereoselectivity(Z:E=89-62:11-38).

  9. Glucose-lowering Activity of Amino Acid-N-phosphonic Acid Oxovanadium Complexes and Its Interaction with DNA

    Institute of Scientific and Technical Information of China (English)

    LIU, Ju-Tao; FAN, Sheng-Di; LI, Chuan-Bi; LI, De-Qian

    2006-01-01

    Vanadium has well-documented lowering glucose properties both in vitro and in vivo. The design of new oxovanadium(Ⅳ) coordination compounds, intended for use as insulin-enhancing agents in the treatment of diabetes mellitus, can potentially benefit from a synergistic approach, in which the whole complex has more than an additive effect from its component parts. Biological testing with oxovanadium(Ⅳ) organic phosphonic acid, for insulin-enhancing potential included acute administration, by oral gavage in streptozotocin (STZ) diabetic rats. The complexes of oxovanadium(Ⅳ) amino acid-N-phosphonic acid exhibit higher lowering glucose activity in vivo. The interaction of the complexes of oxovanadium(Ⅳ) amino acid-N-phosphonic acid with DNA was investigated by agarose gel electrophoresis. The results indicated that these complexes have strong interaction with DNA.

  10. Discovery of the antibiotic phosacetamycin via a new mass spectrometry-based method for phosphonic acid detection.

    Science.gov (United States)

    Evans, Bradley S; Zhao, Changming; Gao, Jiangtao; Evans, Courtney M; Ju, Kou-San; Doroghazi, James R; van der Donk, Wilfred A; Kelleher, Neil L; Metcalf, William W

    2013-05-17

    Naturally occurring phosphonates such as phosphinothricin (Glufosinate, a commercially used herbicide) and fosfomycin (Monurol, a clinically used antibiotic) have proved to be potent and useful biocides. Yet this class of natural products is still an under explored family of secondary metabolites. Discovery of the biosynthetic pathways responsible for the production of these compounds has been simplified by using gene based screening approaches, but detection and identification of the natural products the genes produce have been hampered by a lack of high-throughput methods for screening potential producers under various culture conditions. Here, we present an efficient mass-spectrometric method for the selective detection of natural products containing phosphonate and phosphinate functional groups. We have used this method to identify a new phosphonate metabolite, phosacetamycin, whose structure, biological activity, and biosynthetic gene cluster are reported.

  11. Methods for neutralizing anthrax or anthrax spores

    Science.gov (United States)

    Sloan, Mark A; Vivekandanda, Jeevalatha; Holwitt, Eric A; Kiel, Johnathan L

    2013-02-26

    The present invention concerns methods, compositions and apparatus for neutralizing bioagents, wherein bioagents comprise biowarfare agents, biohazardous agents, biological agents and/or infectious agents. The methods comprise exposing the bioagent to an organic semiconductor and exposing the bioagent and organic semiconductor to a source of energy. Although any source of energy is contemplated, in some embodiments the energy comprises visible light, ultraviolet, infrared, radiofrequency, microwave, laser radiation, pulsed corona discharge or electron beam radiation. Exemplary organic semiconductors include DAT and DALM. In certain embodiments, the organic semiconductor may be attached to one or more binding moieties, such as an antibody, antibody fragment, or nucleic acid ligand. Preferably, the binding moiety has a binding affinity for one or more bioagents to be neutralized. Other embodiments concern an apparatus comprising an organic semiconductor and an energy source. In preferred embodiments, the methods, compositions and apparatus are used for neutralizing anthrax spores.

  12. Crystal structure and characterization of a novel layered copper-lithium phosphonate with antiferromagnetic intrachain Cu(II)···Cu(II) interactions

    Science.gov (United States)

    Abdelbaky, Mohammed S. M.; Amghouz, Zakariae; Blanco, David Martínez; García-Granda, Santiago; García, José R.

    2017-04-01

    Novel metal phosphonate [CuLi(PPA)] [H3PPA=3-phosphonopropionic acid] was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. It crystallizes in the space group C2/c, with cell parameters a=21.617(2) Å, b=4.9269(2) Å, c=14.342(1) Å, β=132.3(2)°, and Z=8. Its framework is built up from a main trimer, acting as a secondary building unit (SBU), which is formed by vertex-shared between two {LiO4} and one {Cu(1)O4} polyhedra. These units repeat along b-axis forming infinite inorganic chains, these chains are in turn cross-linked by corner sharing with {Cu(2)O4} polyhedra to produce inorganic layers lying in the bc-plane. The neighboring layers are connected through the PPA ligand, leading to a 3D pillared-layered structure. The topological analysis reveals that the compound exhibits 3,4,10-c net. Finally, magnetic susceptibility measurement of this compound over the temperature range of 2-300 K reveals the occurrence of weak antiferromagnetic intrachain interactions.

  13. The Effects of Phosphonic Acids in Dye-Sensitized Solar Cells

    Science.gov (United States)

    James, Keith Edward

    Novel methods for the construction of dye-sensitized solar cells (DSSCs) were developed. A thin dense underlayer of TiO2 was applied on fluorine-doped tin oxide (FTO) glass using as a precursor Tyzor AA-105. Subsequently a mesoporous film of P-25 TiO2 was applied by spreading a suspension uniformly over the surface of the underlayer and allowing the plate to slowly dry while resting on a level surface. After sintering at 500° C slides were treated with TCPP as a sensitizing dye and assembled into DSSCs. A novel method was used to seal the cells; strips of ParafilmRTM were used as spacers between the electrodes and to secure the electrodes together. The cells were filled with a redox electrolyte and sealed by dipping into molten paraffin. A series of phosphonic acids and one arsonic acid were employed as coadsorbates in DSSCs. The coadsorbates were found to compete for binding sites, resulting in lower levels of dye adsorption. The resulting loss of photocurrent was not linear with the reduction of dye loading, and in some cases photocurrent and efficiency were higher for cells with lower levels of dye loading. Electrodes were treated with coadsorbates by procedures including pre-adsorption, simultaneous (sim-adsorption), and post-adsorption, using a range of concentrations and treatment times and a variety of solvents. Most cells were tested using an iodide-triiodide based electrolyte (I3I-1) but some cells were tested using electrolytes based on a Co(II)/Co(III) redox couple (CoBpy electrolytes). Phosphonic acid post-adsorbates increased the Voc of cells using CoBpy electrolytes but caused a decrease in the Voc of cells using I3I-1 electrolyte. Phosphonic acids as sim-adsorbates resulted in a significant increase in efficiency and Jsc, and they show promise as a treatment for TCPP DSSCs.

  14. Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

    Science.gov (United States)

    Rueff, Jean-Michel; Poienar, Maria; Guesdon, Anne; Martin, Christine; Maignan, Antoine; Jaffrès, Paul-Alain

    2016-04-01

    Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containing phosphonates organic building units crystallizing in different structural types.

  15. Synthesis of New Lipophilic Phosphonate and Phosphonamidate Analogues of N-Acetylmuramyl-L-alanyl-D-isoglutamine Related to LK 423

    Directory of Open Access Journals (Sweden)

    Uroš Urleb

    2002-05-01

    Full Text Available A syntheses of three new muramyl dipeptide (MDP analogues related to LK 423 as potential immunomodulators are presented. The dipeptide part of the lead compound was modified by introducing a phosphonamide isostere instead of the amide bond between Lalanine and D-glutamic acid (or D-isoglutamine, yielding new MDP analogues 5 and 9. Furthermore, the amide bond between L-Ala and D-Glu was replaced by a phosphonate isostere, giving peptidyl phosphonate 14. The scope and limitations of the synthetic strategies employed are discussed.

  16. Zirconium phosphonate/1,4,5,8-naphthalenediimides self-assembled films

    Directory of Open Access Journals (Sweden)

    MAGALI A. RODRIGUES

    2000-03-01

    Full Text Available The formation and characterization of self-assembled films of zirconium phosphonate / N,N'-di(2-phosphonoethyl-1,4,5,8-naphthalenediimide (DPN is presented. The films were produced on glass substrates by deposition of alternating layers of Zr+4 and DPN. Films containing up to 16 layers on each side of the substrate were obtained and monitored by absorption spectroscopy and ellipsometry. When irradiated, the initially colorless films turned to a persistent pinky color reminiscent of that of DPN anion radical. These films are a promising material to the development of photovoltaic devices.

  17. Sustainable Catalytic Process for Synthesis of Triethyl Citrate Plasticizer over Phosphonated USY Zeolite

    Directory of Open Access Journals (Sweden)

    Kakasaheb Y. Nandiwaleand

    2016-10-01

    Full Text Available Fruits wastage is harmful to health and environment concerning spreading diseases and soil pollution, respectively. To avoid this issue, use of citrus fruit waste for the production of citric acid (CA is one of viable mean to obtain value added chemicals. Moreover, synthesis of triethyl citrate (TEC, a non-toxic plasticizer by esterification of CA with ethanol over heterogeneous catalyst would be renewable and sustainable catalytic process. In this context, parent Ultrastable Y (USY and different percentage phosphonated USY (P-USY zeolites were used for the synthesis of TEC in a closed batch reactor, for the first time. The synthesized catalysts were characterized by N2-adsorption desorption isotherm, powder X-ray diffraction (XRD and NH3 temperature programmed desorption (TPD. Effect of reaction conditions, such as the molar ratio of ethanol to CA (5:1 - 20:1, the catalyst to CA ratio (0.05 - 0.25 and reaction temperature (363-403 K, were studied in view to maximizing CA conversion and TEC yield. Phosphonated USY catalysts were found to be superior in activity (CA conversion and TEC yield than parent USY, which is attributed to the increased in total acidity with phosphonation. Among the studied catalysts, the P2USY (2% phosphorous loaded on USY was found to be an optimum catalyst with 99% CA conversion and 82% TEC yield, which is higher than the reported values. This study opens new avenues of research demonstrating principles of green chemistry such as easy separable and reusable catalyst, non-toxic product, bio-renewable synthetic route, milder operating parameters and waste minimization. Copyright © 2016 BCREC GROUP. All rights reserved Received: 12nd October 2015; Revised: 22nd December 2015; Accepted: 29th January 2016 How to Cite: Nandiwale, K.Y., Bokade, V.V. (2016. Sustainable Catalytic Process for Synthesis of Triethyl Citrate Plasticizer over Phosphonated USY Zeolite. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 292

  18. 1-Ammonio-1-phosphono-pentane-1-phospho-nic acid.

    Science.gov (United States)

    Bon, V V; Dudko, A V; Kozachkova, A N; Pekhnyo, V I

    2008-11-26

    The title compound, C(5)H(15)NO(6)P(2), was obtained by the reaction of penta-nenitrile with PCl(3) followed by the dropwise addition of water. The asymmetric unit contains one mol-ecule, which exists as a zwitterion with a positive charge on the -NH(3) group and a negative charge on one of the phospho-nic O atoms. The crystal structure displays N-H⋯O and O-H⋯O hydrogen bonding, which creates a three-dimensional network.

  19. Uranyl-selective electrodes based on acyclic oligoethers with terminal phosphonate groups

    Energy Technology Data Exchange (ETDEWEB)

    Khramov, A.N.; Garifzyanov, A.R.; Toropova, V.F. [Kazan State Univ., Tatarstan (Russian Federation)

    1994-10-01

    In recent years, a number of attempts have been made to develop ion-selective electrodes sensitive to uranyl ions. The most appropriate ionophores for uranyl-selective electrodes have been found among both acyclic oligoethers (podands) with terminal amide groups and organophosphorous compounds (conventional extracting agents for uranyl salts). However, in the first case, the proposed uranyl-selective electrodes exhibit a linear electrode response in a rather narrow range; in the second case, the electrodes are insufficiently selective. The goal of this work was to examine the possibility of using podands with terminal phosphonate groups as ionophores in uranyl-selective electrodes.

  20. A sustainable and efficient synthesis of benzyl phosphonates using PEG/KI catalytic system

    Science.gov (United States)

    Gawande, Manoj; Disale, Shamrao; Kale, Sandip; Abraham, George; Kahandal, Sandeep; Sawarkar, Ashish

    2016-08-01

    An efficient and expedient protocol for the synthesis of benzyl phosphonates using KI/K2CO3 as a catalytic system and PEG-400 as benign solvent has been developed. The reaction proceeds smoothly at room temperature achieving excellent selectivity and yield of the corresponding products. The combination of PEG-400, KI and K2CO3 in this reaction avoids the need of volatile/toxic organic solvents and reactive alkali metals or metal nanoparticles/hydrides. We believe that this benign combination (PEG-400 and KI) could be used for other related organic transformations.

  1. A sustainable and efficient synthesis of benzyl phosphonates using PEG/KI catalytic system

    Directory of Open Access Journals (Sweden)

    Manoj B. Gawande

    2016-08-01

    Full Text Available An efficient and expedient protocol for the synthesis of benzyl phosphonates using KI/K2CO3 as a catalytic system and PEG-400 as benign solvent has been developed. The reaction proceeds smoothly at room temperature achieving excellent selectivity and yield of the corresponding products. The combination of PEG-400, KI and K2CO3 in this reaction avoids the need of volatile/toxic organic solvents and reactive alkali metals or metal nanoparticles/hydrides. We believe that this benign combination (PEG-400 and KI could be used for other related organic transformations.

  2. Synthesis, Cu(II) complexation, 64Cu-labeling and biological evaluation of cross-bridged cyclam chelators with phosphonate pendant arms.

    Science.gov (United States)

    Ferdani, Riccardo; Stigers, Dannon J; Fiamengo, Ashley L; Wei, Lihui; Li, Barbara T Y; Golen, James A; Rheingold, Arnold L; Weisman, Gary R; Wong, Edward H; Anderson, Carolyn J

    2012-02-21

    A new class of cross-bridged cyclam-based macrocycles featuring phosphonate pendant groups has been developed. 1,4,8,11-tetraazacyclotetradecane-1,8-di(methanephosphonic acid) (CB-TE2P, 1) and 1,4,8,11-tetraazacyclotetradecane-1-(methanephosphonic acid)-8-(methanecarboxylic acid) (CB-TE1A1P, 2) have been synthesized and have been shown to readily form neutral copper(II) complexes at room temperature as the corresponding dianions. Both complexes showed high kinetic inertness to demetallation and crystal structures confirmed complete encapsulation of copper(II) ion within each macrocycle's cleft-like structure. Unprecedented for cross-bridged cyclam derivatives, both CB-TE2P (1) and CB-TE1A1P (2) can be radiolabeled with (64)Cu at room temperature in less than 1 h with specific activities >1 mCi μg(-1). The in vivo behavior of both (64)Cu-CB-TE2P and (64)Cu-CB-TE1A1P were investigated through biodistribution studies using healthy male Lewis rats. Both new compounds showed rapid clearance with similar or lower accumulation in non-target organs/tissues when compared to other copper chelators including CB-TE2A, NOTA and Diamsar.

  3. Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

    Directory of Open Access Journals (Sweden)

    Kui-Rong Ma

    2013-01-01

    Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

  4. Structure based design, synthesis and biological evaluation of amino phosphonate derivatives as human glucokinase activators.

    Science.gov (United States)

    Yellapu, Nanda Kumar; Kilaru, Ravendra Babu; Chamarthi, Nagaraju; Pvgk, Sarma; Matcha, Bhaskar

    2017-06-01

    Glucokinase (GK) is a potential therapeutic target of type 2 diabetes and GK activators (GKAs) represent a promising class of small organic molecules which enhance GK activity. Based on the configuration and conformation of the allosteric site of GK, we have designed a novel class of amino phosphonate derivatives in order to develop potent GKAs. The QSAR model developed using numerous descriptors revealed its potential with the best effective statistical values of RMSE=1.52 and r(2)=0.30. Moreover, application of this model on the present test set GKAs proved to be worthy to predict their activities as a better linear relationship was observed with RMSE=0.14 and r(2)=0.88. ADME studies and Lipinski filters encouraged them as safer therapeutics. The molecular dynamics and docking studies against the GK allosteric site revealed that all GKAs bind with best affinities and the complexes are strengthened by H-bonding, phosphonate salt bridges, hydrophobic and arene cat ionic interactions. Finally, in vitro evaluation with human liver GK revealed their potential to increase the GK activity by different folds. The results from QSAR, ADME, molecular docking and in vitro assays strongly suggested that the present molecules could be used as effective and safer therapeutics to control and manage type 2 diabetes. Copyright © 2017. Published by Elsevier Ltd.

  5. Differential effects of phosphonic analogues of GABA on GABA(B) autoreceptors in rat neocortical slices.

    Science.gov (United States)

    Ong, J; Marino, V; Parker, D A; Kerr, D I

    1998-04-01

    The effects of five phosphonic derivatives of GABA on the release of [3H]-GABA from rat neocortical slices, preloaded with [3H]-GABA, were investigated. Phaclofen and 4-aminobutylphosphonic acid (4-ABPA) increased the overflow of [3H] evoked by electrical stimulation (2 Hz) in a concentration-dependent manner, with similar potencies (phaclofen EC50=0.3 mmol/l, 4-ABPA EC50=0.4 mmol/l). At 3 mmol/l, phaclofen increased the release of [3H]-GABA by 82.6+/-8.6%, and 4-ABPA increased the release by 81.3+/-9.0%. 2-Amino-ethylphosphonic acid (2-AEPA) increased the overflow of [3H] by 46.8+/-10.9% at the highest concentration tested (3 mmol/l). In contrast, the lower phosphonic homologue 3-aminopropylphosphonic acid (3-APPA), and 2-amino-2-(p-chlorophenyl)-ethylphosphonic acid (2-CPEPA), a baclofen analogue, did not modify the stimulated overflow. These results suggest that phaclofen, 4-ABPA and 2-AEPA are antagonists at GABA(B) autoreceptors, the latter being the weakest antagonist, whilst neither 3-APPA nor 2-CPEPA are active at these receptors. Since phaclofen, 4-ABPA and 2-CPEPA are antagonists and 3-APPA a partial agonist/antagonist on GABA(B) heteroreceptors, the lack of effect of 3-APPA and 2-CPEPA on [3H]-GABA release in this study suggests that GABA(B) autoreceptors may be pharmacologically distinct from the heteroreceptors.

  6. Formation of phosphonates and pyrophosphates in the reactions of chlorophosphate esters with strong organic bases

    Indian Academy of Sciences (India)

    K V P Pavan Kumar; K Praveen Kumar; M Vijjulatha; K C Kumara Swamy

    2004-11-01

    The compounds S(6--Bu-4-Me-C6H2O)2P(O)Cl (1), CH2(6--Bu-4-Me-C6H2O)2P(O)Cl (2) and (2,2'-C20H12O2)P(O)Cl (3) react with diazabicycloundecene (DBU) to give rise to, predominantly, the phosphonate compounds [S(6--Bu-4-Me-C6H2O)2P(O)(DBU)]+[Cl]- (4), [CH2(6--Bu-4-Me-C6H2O)2P(O) (DBU)]+[Cl]- (5) and [(2,2'-C20H12O2)P(O)(DBU)]+[Cl]- (6). The first two compounds could be isolated in the pure state. In analogous reactions of 1 and 2 with diazabicyclononene (DBN) or N-methyl imidazole, only the pyrophosphates [S(6--Bu-4-Me-C6H2O)2P(O)]2O (7) and [CH2(6--Bu-4-Me-C6H2O)2P(O)]2O (8) could be isolated, although the reaction mixture showed several other compounds in the phosphorus NMR. A possible pathway for the formation of phosphonate salts is proposed. The X-ray crystal structures of 4, 7 and 8 are also discussed.

  7. Heavyweight "R-SMS-Phos" ligands in the olefins' hydrogenation arena.

    Science.gov (United States)

    Zupancic, Borut; Mohar, Barbara; Stephan, Michel

    2010-03-19

    A series of enantiopure P-stereogenic 1,2-bis[(o-RO-phenyl)(phenyl)phosphino]ethane (R-SMS-Phos) ligands wherein R = i-Pr, i-Bu, t-Bu, 3-Pen, and CH(2)TMS was assessed in the Rh(I)-catalyzed hydrogenation of an indicative set of olefins. The best performing t-Bu-SMS-Phos ligand was screened against a wide range of representative classes of standard and new olefinic substrates such as dehydroamido esters, dehydro-alpha-amido-phosphonates, enamides, itaconates, acrylates, enol acetates, alpha-phosphonovinyl benzoates, alpha-(2-pyridyl N-oxide)styrenes, and alpha-(1-hydroxyliminoethyl)styrenes. Excellent enantioselectivities and high TOFs were attained under mild conditions.

  8. [Enzymatic activity of thymidine kinase of herpes simlex virus strain resistant to H-phosphonates of Acv].

    Science.gov (United States)

    Gus'kova, A A; Skoblov, M Iu; Andronova, V L; Galegov, G A; Kochetkov, S N; Skoblov, Iu S

    2011-01-01

    Cloned laboratory mutants of herpes simplex virus type I resistant to acycloguanosine H-phosphonate have been investigated. For all clones were shown that mutations resulted to increasing of sensitivity to acting of sidofovir. Thymidine kinase of mutant viruses partially preserves the ability to phosphorilate thymidine, but loses the ability to phosphorilate BVDU.

  9. Tuning the field-induced magnetic transition in a layered cobalt phosphonate by reversible dehydration-hydration process.

    Science.gov (United States)

    Yang, Ting-Hai; Liao, Yi; Zheng, Li-Min; Dinnebier, Robert E; Su, Yan-Hui; Ma, Jing

    2009-06-07

    A layered cobalt phosphonate, Co(2-pmp)(H(2)O)(2) (1) (2-pmpH(2) = 2-pyridylmethylphosphonic acid) is reported, which provides the first example of metamagnetic cobalt system that shows reversible changes in both structures and magnetic behaviors upon dehydration-hydration process.

  10. Neutralization of English Consonants

    Institute of Scientific and Technical Information of China (English)

    庞彬彬

    2011-01-01

    This paper gives a brief account of English consonant cluster's structure and phonetic features from the perspective of the definition and cause of neutralization of English consonants as well as their distinctive features and oppositions.It comes up with the final conclusion that neutralization exists in only thirteen English consonant clusters,among a large number of consonant clusters.

  11. A ladder coordination polymer based on Ca(2+) and (4,5-dicyano-1,2-phenylene)bis(phosphonic acid): crystal structure and solution-state NMR study.

    Science.gov (United States)

    Venkatramaiah, Nutalapati; Mendes, Ricardo F; Silva, Artur M S; Tomé, João P C; Almeida Paz, Filipe A

    2016-09-01

    The preparation of coordination polymers (CPs) based on either transition metal centres or rare-earth cations has grown considerably in recent decades. The different coordination chemistry of these metals allied to the use of a large variety of organic linkers has led to an amazing structural diversity. Most of these compounds are based on carboxylic acids or nitrogen-containing ligands. More recently, a wide range of molecules containing phosphonic acid groups have been reported. For the particular case of Ca(2+)-based CPs, some interesting functional materials have been reported. A novel one-dimensional Ca(2+)-based coordination polymer with a new organic linker, namely poly[[diaqua[μ4-(4,5-dicyano-1,2-phenylene)bis(phosphonato)][μ3-(4,5-dicyano-1,2-phenylene)bis(phosphonato)]dicalcium(II)] tetrahydrate], {[Ca2(C8H4N2O6P2)2(H2O)2]·4H2O}n, has been prepared at ambient temperature. The crystal structure features one-dimensional ladder-like ∞(1)[Ca2(H2cpp)2(H2O)2] polymers [H2cpp is (4,5-dicyano-1,2-phenylene)bis(phosphonate)], which are created by two distinct coordination modes of the anionic H2cpp(2-) cyanophosphonate organic linkers: while one molecule is only bound to Ca(2+) cations via the phosphonate groups, the other establishes an extra single connection via a cyano group. Ladders close pack with water molecules through an extensive network of strong and highly directional O-H...O and O-H...N hydrogen bonds; the observed donor-acceptor distances range from 2.499 (5) to 3.004 (6) Å and the interaction angles were found in the range 135-178°. One water molecule was found to be disordered over three distinct crystallographic positions. A detailed solution-state NMR study of the organic linker is also provided.

  12. A Green Approach to the Synthesis of α-Amino Phosphonate in Water Medium: Carbene Insertion into the N-H Bond by Cu(I) Catalyst.

    Science.gov (United States)

    Ramakrishna, Kankanala; Thomas, Jisha Mary; Sivasankar, Chinnappan

    2016-10-21

    Synthesis of amino phosphonates is more important owing to their significant applications in the biological systems. There are few methods already known in the literature to make these molecules; however, known methods have their own disadvantages. In this regard, synthesis of different kinds of amino phosphonates have been achieved via phosphonate substituted carbene insertion into the N-H bond of aniline catalyzed by readily available copper salt under mild reaction conditions in water. In order to find an efficient catalyst for carbene insertion reaction in neat water, a large number of transition metal catalysts were screened, and we found that the [Cu(CH3CN)4]ClO4 was the best catalyst under employed reaction conditions. Using this environmentally benign methodology (copper catalyzed reaction in water), a large number of biologically important amino phosphonates have been synthesized, isolated (37 examples), and characterized using standard analytical and spectroscopic techniques.

  13. Proton transport properties of tin phosphate, chromotropic acid anchored onto tin phosphate and tin phenyl phosphonate

    Indian Academy of Sciences (India)

    Chithra Sumej; P P Sharmila; Nisha J Tharayil; S Suma

    2013-02-01

    Tin (IV) phosphates of the class of tetravalent metal acid (TMA) salts have been synthesized by sol–gel method. The functionalized materials of tin (IV) phosphate (SnP) like chromotropic acid anchored tin phosphate (SnPCA) and tin phenyl phosphonate (SnPP) were also synthesized. These materials have been characterized for elemental analysis (ICP–AES), thermal analysis, X-ray analysis and FTIR spectroscopy. Chemical resistivity of these materials has been accessed in acidic, basic and organic solvent media. The proton present in the structural hydroxyl groups indicates good potential for TMA salts to exhibit solid-state proton conduction. The transport properties of these materials have been explored by measuring specific proton conductance at different temperatures. Based on the specific conduction data and Arrhenius plots, a suitable mechanism has been proposed.

  14. Surface modification of hydroxyapatite nanocrystals by grafting polymers containing phosphonic acid groups.

    Science.gov (United States)

    Choi, Hyung Woo; Lee, Hong Jae; Kim, Kyung Ja; Kim, Hyun-Min; Lee, Sang Cheon

    2006-12-01

    A novel approach for the surface modification of hydroxyapatite (HAp) nanocrystals is described by grafting polymerization of vinyl phosphonic acid (VPA) using a redox initiating system in an aqueous media. Fourier transform infrared (FT-IR) and XRD analyses confirmed the modification reaction on HAp surfaces. Inductively coupled plasma mass spectroscopy (ICP MS) showed that the Ca/P molar ratio decreased from 1.67 to 1.36 with increasing the feed VPA amount. Zeta potentials of unmodified HAp and modified HAp in phosphate-buffered saline (PBS) solutions (pH 7.4, ionic strength = 10 mM) were negative and decreased with increasing the amount of grafted PVPA. Transmission electron microscopy (TEM) measurements and time-dependent phase monitoring indicated that the colloidal stability of modified HAp over unmodified HAp in water dramatically increased and tended to exist as single nanocrystals without aggregation.

  15. Acyclic Immucillin Phosphonates. Second-Generation Inhibitors of Plasmodium falciparum Hypoxanthine- Guanine-Xanthine Phosphoribosyltransferase

    Energy Technology Data Exchange (ETDEWEB)

    Hazelton, Keith Z. [Yeshiva Univ., New York, NY (United States); Ho, Meng-Chaio [Yeshiva Univ., New York, NY (United States); Cassera, Maria B. [Yeshiva Univ., New York, NY (United States); Clinch, Keith [Industrial Research Ltd., Lower Hutt (New Zealand); Crump, Douglas R. [Industrial Research Ltd., Lower Hutt (New Zealand); Rosario Jr., Irving [Yeshiva Univ., New York, NY (United States); Merino, Emilio F. [Yeshiva Univ., New York, NY (United States); Almo, Steve C. [Yeshiva Univ., New York, NY (United States); Tyler, Peter C. [Industrial Research Ltd., Lower Hutt (New Zealand); Schramm, Vern L. [Yeshiva Univ., New York, NY (United States)

    2012-06-22

    We found that Plasmodium falciparum is the primary cause of deaths from malaria. It is a purine auxotroph and relies on hypoxanthine salvage from the host purine pool. Purine starvation as an antimalarial target has been validated by inhibition of purine nucleoside phosphorylase. Hypoxanthine depletion kills Plasmodium falciparum in cell culture and in Aotus monkey infections. Hypoxanthine-guanine-xanthine phosphoribosyltransferase (HGXPRT) from P. falciparum is required for hypoxanthine salvage by forming inosine 5'-monophosphate, a branchpoint for all purine nucleotide synthesis in the parasite. We present a class of HGXPRT inhibitors, the acyclic immucillin phosphonates (AIPs), and cell permeable AIP prodrugs. The AIPs are simple, potent, selective, and biologically stable inhibitors. The AIP prodrugs block proliferation of cultured parasites by inhibiting the incorporation of hypoxanthine into the parasite nucleotide pool and validates HGXPRT as a target in malaria.

  16. Synthesis, Cytotoxicity, DNA Binding and Apoptosis of Rhein-Phosphonate Derivatives as Antitumor Agents

    Directory of Open Access Journals (Sweden)

    Man-Yi Ye

    2013-04-01

    Full Text Available Several rhein-phosphonate derivatives (5a–c were synthesized and evaluated for in vitro cytotoxicity against HepG-2, CNE, Spca-2, Hela and Hct-116 cell lines. Some compounds showed relatively high cytotoxicity. Especially compounds 5b exhibited the strongest cytotoxicity against HepG-2 and Spca-2 cells (IC50 was 8.82 and 9.01 µM, respectively. All the synthesized compounds exhibited low cytotoxicity against HUVEC cells. Further experiments proved that 5b could disturb the cell cycle in HepG-2 cells and induce apoptosis. In addition, the binding properties of a model conjugate 5b to DNA were investigated by methods (UV-Vis, fluorescence, CD spectroscopy. Results indicated that 5b showed moderate ability to interact ct-DNA.

  17. Ether lipid-ester prodrugs of acyclic nucleoside phosphonates: activity against adenovirus replication in vitro.

    Science.gov (United States)

    Hartline, Caroll B; Gustin, Kortney M; Wan, William B; Ciesla, Stephanie L; Beadle, James R; Hostetler, Karl Y; Kern, Earl R

    2005-02-01

    The acyclic nucleoside phosphonate cidofovir (CDV) and its closely related analogue (S)-9-(3-hydroxy-2-phosphonylmethoxypropyl)-adenine ([S]-HPMPA) have been reported to have activity against many adenovirus (AdV) serotypes. A new series of orally active ether lipid-ester prodrugs of CDV and of (S)-HPMPA that have slight differences in the structure of their lipid esters were evaluated, in tissue-culture cells, for activity against 5 AdV serotypes. The results indicated that, against several AdV serotypes, the most active compounds were 15-2500-fold more active than the unmodified parent compounds and should be evaluated further for their potential to treat AdV infections in humans.

  18. Alpha-heteroatom derivatized analogues of 3-(acetylhydroxyamino)propyl phosphonic acid (FR900098) as antimalarials.

    Science.gov (United States)

    Verbrugghen, Thomas; Vandurm, Pierre; Pouyez, Jenny; Maes, Louis; Wouters, Johan; Van Calenbergh, Serge

    2013-01-10

    To explore the hitherto successful derivatization of the α-carbon of fosmidomycin, a series of new α-substituted analogues was prepared. This was done by introduction of a heteroatom (N or O) in α-position to the phosphonate and using the resultant OH and NH₂ groups as a handle for appending a variety of substituents by means of several functional groups such as ether, amide, urea, and 1,4-triazole. The synthesized molecules, as a racemic mixture, were assayed for their EcDXR inhibitory potency. Both the α-azido-analogue and the α-hydroxylated analogue proved most promising, and docking experiments were performed. Although several compounds showed high potency when assayed against Plasmodium falciparum K1 in human erythrocytes, a clear correlation between the enzyme inhibition constants and P. falciparum inhibition concentrations could not be found.

  19. Phosphonic acid functionalized asymmetric phthalocyanines: synthesis, modification of indium tin oxide, and charge transfer.

    Science.gov (United States)

    Polaske, Nathan W; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayunk; Oquendo, Luis E; Green, John T; Ratcliff, Erin L; Armstrong, Neal R; Saavedra, S Scott; McGrath, Dominic V

    2011-12-20

    Metalated and free-base A(3)B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  20. Phosphonic Acid Functionalized Asymmetric Phthalocyanines: Synthesis, Modification of Indium Tin Oxide (ITO), and Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Polaske, Nathan W.; Lin, Hsiao-Chu; Tang, Anna; Mayukh, Mayank; Oquendo, Luis E.; Green, John; Ratcliff, Erin L.; Armstrong, Neal R.; Saavedra, S. Scott; McGrath, Dominic V.

    2011-12-20

    Metalated and free-base A₃B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.

  1. New synthesis of silver phosphonate complexes from polymeric silver phenylethynide as a structure-directing precursor.

    Science.gov (United States)

    Xie, Yun-Peng; Mak, Thomas C W

    2013-09-28

    Three new silver(I) phosphonate complexes have been synthesized from silver phenylethynide as a structure-directing precursor. Ag2(PhPO3)(H2O) displays a layer-type coordination network, Ag(3,5-dimethylpyrazole)2(PhPO3H) contains a dimeric unit, and {Ag8(dppm)4((t)BuPO3)2(ClO4)(NO3)(0.67)(H2O)(1.33)}·(ClO4)(2.33)·(CH3OH)(6.67) features an octanuclear composite cluster. We have also isolated the pyrophenylphosphonate complex Ag2[PhPO2(O)O2PPh](CH3CN), which exhibits an infinite-chain structure.

  2. A copper(I)-catalyzed three-component domino process: assembly of complex 1,2,3-triazolyl-5-phosphonates from azides, alkynes, and H-phosphates.

    Science.gov (United States)

    Li, Lingjun; Hao, Guoliang; Zhu, Anlian; Fan, Xincui; Zhang, Guisheng; Zhang, Lihe

    2013-10-18

    Three is better than one! A new copper-catalyzed tricomponent reaction of a terminal alkyne, organic azide, and H-phosphate (CuAA[P]C) leads to a structurally diverse polysubstituted 1,2,3-triazolyl-5-phosphonate, which provides an efficient tool for the direct introduction of phosphonic acid groups by a "click reaction". Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Pharmaceutical and clinical development of phosphonate-based radiopharmaceuticals for the targeted treatment of bone metastases.

    Science.gov (United States)

    Lange, Rogier; Ter Heine, Rob; Knapp, Russ Ff; de Klerk, John M H; Bloemendal, Haiko J; Hendrikse, N Harry

    2016-10-01

    Therapeutic phosphonate-based radiopharmaceuticals radiolabeled with beta, alpha and conversion electron emitting radioisotopes have been investigated for the targeted treatment of painful bone metastases for >35years. We performed a systematic literature search and focused on the pharmaceutical development, preclinical research and early human studies of these radiopharmaceuticals. The characteristics of an ideal bone-targeting therapeutic radiopharmaceutical are presented and compliance with these criteria by the compounds discussed is verified. The importance of both composition and preparation conditions for the stability and biodistribution of several agents is discussed. Very few studies have described the characterization of these products, although knowledge on the molecular structure is important with respect to in vivo behavior. This review discusses a total of 91 phosphonate-based therapeutic radiopharmaceuticals, of which only six agents have progressed to clinical use. Extensive clinical studies have only been described for (186)Re-HEDP, (188)Re-HEDP and (153)Sm-EDTMP. Of these, (153)Sm-EDTMP represents the only compound with worldwide marketing authorization. (177)Lu-EDTMP has recently received approval for clinical use in India. This review illustrates that a thorough understanding of the radiochemistry of these agents is required to design simple and robust preparation and quality control methods, which are needed to fully exploit the potential benefits of these theranostic radiopharmaceuticals. Extensive biodistribution and dosimetry studies are indispensable to provide the portfolios that are required for assessment before human administration is possible. Use of the existing knowledge collected in this review should guide future research efforts and may lead to the approval of new promising agents.

  4. Phosphonate surfactants

    Directory of Open Access Journals (Sweden)

    Pablo C. Schulz

    2003-01-01

    Full Text Available Revisión crítica de las propiedades fisicoquímicas de los tensoactivos derivados de ácidos n-alcano fosfónicos, con especial énfasis en las propiedades de dichos ácidos y de sus sales mono y disódicas, tanto en forma anhidra como en sus sistemas acuosos y en mezclas cataniónicas. Discusión de los cambios en propiedades fisicoquímicas derivadas de la posibilidad de cambiar la carga del grupo polar desde 0 hasta -2, sin modificar la estructura del mismo, y algunas consecuencias que surgen de la estructura de la interfase aire/solución

  5. Tailored control and optimisation of the number of phosphonic acid termini on phosphorus-containing dendrimers for the ex-vivo activation of human monocytes.

    Science.gov (United States)

    Rolland, Olivier; Griffe, Laurent; Poupot, Mary; Maraval, Alexandrine; Ouali, Armelle; Coppel, Yannick; Fournié, Jean-Jacques; Bacquet, Gérard; Turrin, Cédric-Olivier; Caminade, Anne-Marie; Majoral, Jean-Pierre; Poupot, Rémy

    2008-01-01

    The syntheses of a series of phosphonic acid-capped dendrimers is described. This collection is based on a unique set of dendritic structural parameters-cyclo(triphosphazene) core, benzylhydrazone branches and phosphonic acid surface-and was designed to study the influence of phosphonate (phosphonic acid) surface loading towards the activation of human monocytes ex vivo. Starting from the versatile hexachloro-cyclo(triphosphazene) N(3)P(3)Cl(6), six first-generation dendrimers were obtained, bearing one to six full branches, that lead to 4, 8, 12, 16, 20 and 24 phosphonate termini, respectively. The surface loading was also explored at the limit of dense packing by means of a first-generation dendrimer having a cyclo(tetraphosphazene) core and bearing 32 termini, and with a first-generation dendrimer based on a AB(2)/CD(5) growing pattern and bearing 60 termini. Human monocyte activation by these dendrimers confirms the requirement of the whole dendritic structure for bioactivity and identifies the dendrimer bearing four branches, thus 16 phosphonate termini, as the most bioactive.

  6. PHOSPHONYLATION DES COMPOSES A LIAISONS C=X : ACCES AUX Bis-PHOSPHONATES ET ETUDES DE LEURS DE LEURS FONCTIONNALISATIOS.

    OpenAIRE

    EPENIT, MONDJO RODY-DAVY

    2014-01-01

    Dans ce travail, consacré aux bis-phosphonates et iminophosphonates, nous avons tout d'abord, commencé par reproduire un travail sur les bis-phosphonates. Cette opération est bien réussie. Nous avons amélioré cette méthode, en utilisant un processus avec un minimum d'étape. Elle consiste à utiliser les ?-aminoacides sans recours à la protection. Ceci nous fait gagner deux étapes, puisque nous n'aurons pas à débloquer en fin de réaction. C'est à partir de cette méthode que la suite de nos trav...

  7. SBA-15 mesoporous silica free-standing thin films containing copper ions bounded via propyl phosphonate units - preparation and characterization

    Science.gov (United States)

    Laskowski, Lukasz; Laskowska, Magdalena; Jelonkiewicz, Jerzy; Dulski, Mateusz; Wojtyniak, Marcin; Fitta, Magdalena; Balanda, Maria

    2016-09-01

    The SBA-15 silica thin films containing copper ions anchored inside channels via propyl phosphonate groups are investigated. Such materials were prepared in the form of thin films, with hexagonally arranged pores, laying rectilinear to the substrate surface. However, in the case of our thin films, their free standing form allowed for additional research possibilities, that are not obtainable for typical thin films on a substrate. The structural properties of the samples were investigated by X-ray reflectometry, atomic force microscopy (AFM) and transmission electron microscopy (TEM). The molecular structure was examined by Raman spectroscopy supported by numerical simulations. Magnetic measurements (SQUID magnetometry and EPR spectroscopy) showed weak antiferromagnetic interactions between active units inside silica channels. Consequently, the pores arrangement was determined and the process of copper ions anchoring by propyl phosphonate groups was verified in unambiguous way. Moreover, the type of interactions between magnetic atoms was determined.

  8. Neutral particle lithography

    Science.gov (United States)

    Craver, Barry Paul

    Neutral particle lithography (NPL) is a high resolution, proximity exposure technique where a broad beam of energetic neutral particles floods a stencil mask and transmitted beamlets transfer the mask pattern to resist on a substrate, such that each feature is printed in parallel, rather than in the serial manner of electron beam lithography. It preserves the advantages of ion beam lithography (IBL), including extremely large depth-of-field, sub-5 nm resist scattering, and the near absence of diffraction, yet is intrinsically immune to charge-related artifacts including line-edge roughness and pattern placement errors due to charge accumulation on the mask and substrate. In our experiments, a neutral particle beam is formed by passing an ion beam (e.g., 30 keV He+) through a high pressure helium gas cell (e.g., 100 mTorr) to convert the ions to energetic neutrals through charge transfer scattering. The resolution of NPL is generally superior to that of IBL for applications involving insulating substrates, large proximity gaps, and ultra-small features. High accuracy stepped exposures with energetic neutral particles, where magnetic or electrostatic deflection is impossible, have been obtained by clamping the mask to the wafer, setting the proximity gap with a suitable spacer, and mechanically inclining the mask/wafer stack relative to the beam. This approach is remarkably insensitive to vibration and thermal drift; nanometer scale image offsets have been obtained with +/-2 nm placement accuracy for experiments lasting over one hour. Using this nanostepping technique, linewidth versus dose curves were obtained, from which the NPL lithographic blur was determined as 4.4+/-1.4 nm (1sigma), which is 2-3 times smaller than the blur of electron beam lithography. Neutral particle lithography has the potential to form high density, periodic patterns with sub-10 nm resolution.

  9. Synthesis of highly phosphonic acid functionalized benzene-bridged periodic mesoporous organosilicas for use as efficient dye adsorbents

    Energy Technology Data Exchange (ETDEWEB)

    Deka, Juti Rani; Liu, Chia-Ling; Wang, Tzu-Hua; Chang, Wei-Chieh; Kao, Hsien-Ming, E-mail: hmkao@cc.ncu.edu.tw

    2014-08-15

    Highlights: • Synthesis of highly phosphonic acid functionalized benzene-bridged PMOs. • Phosphonic acid loaded PMOs as adsorbent for cationic and anionic dyes. • Due to electrostatic interaction the adsorbent has high dye adsorption capacity. • π–π stacking interaction between benzene and dye enhances adsorption capacity. • Intraparticle diffusion played a dominant role in the adsorption process. - Abstract: Periodic mesoporous organosilicas (PMOs) with benzene bridging groups in the silica wall were functionalized with a tunable content of phosphonic acid groups. These bifunctional materials were synthesized by co-condensation of two different organosilane precursors, that is, 1,4-bis(triethoxysilyl)benzene (BTEB) and sodium 3-(trihydroxysilyl)propyl methyl phosphate (SPMP), under acidic conditions using nonionic surfactant Brij-S10 as template. The materials exhibited well-ordered mesostructures and were characterized by X-ray diffraction, nitrogen sorption, TEM, TGA, FTIR, and solid-state NMR measurements. The materials thus obtained were employed as adsorbents to remove different types of dyes, for example, cationic dyes methylene blue and phenosafranine, anionic orange II, and amphoteric rhodamine B, from aqueous solutions. The materials exhibited a remarkably high adsorption capacity than activated carbon due to their ordered mesostructures, a large number of phosphonic acid groups, and high surface areas. The adsorption was mainly governed by electrostatic interaction, but also involved π–π stacking interaction as well as hydrogen bonding. The adsorption kinetics can be better fitted by the pseudo-second order model. The adsorption process was controlled by the mechanisms of external mass transfer and intraparticle diffusion. The materials retained more than 97% dye removal efficiency after use for five consecutive cycles.

  10. Direct assembly synthesis of metal complex-semiconductor hybrid photocatalysts anchored by phosphonate for highly efficient CO2 reduction.

    Science.gov (United States)

    Suzuki, Tomiko M; Tanaka, Hiromitsu; Morikawa, Takeshi; Iwaki, Masayo; Sato, Shunsuke; Saeki, Shu; Inoue, Masae; Kajino, Tsutomu; Motohiro, Tomoyoshi

    2011-08-14

    Hybrid photocatalysts consisting of a ruthenium complex and p-type photoactive N-doped Ta(2)O(5) anchored with an organic group were successfully synthesized by a direct assembly method. The photocatalyst anchored by phosphonate exhibited excellent photoconversion activity of CO(2) to formic acid under visible-light irradiation with respect to the reaction rate and stability. This journal is © The Royal Society of Chemistry 2011

  11. Substituted ethan phosphonic acid esters as reagents for the separation of molybdenum from rhenium by solvent extraction.

    Science.gov (United States)

    Jordanov, N; Mareva, S; Borisov, G; Jordanov, B

    1968-02-01

    New esters of the ethan phosphonic acids have been synthesized and their extraction properties studied with respect to Mo(VI), Re(VII), Fe(III),Au(III),Tl(III) and Sb(V). A possibility is shown for the analytical separation of molybdenum from rhenium (beta = 700). The state of these new extraction agents in carbon tetrachloride solution, and the mechanism of the extraction processes, have been investigated by means of infrared spectra.

  12. Amphiphilic paramagnetic neutral gold dithiolene complexes.

    Science.gov (United States)

    Perochon, Romain; Piekara-Sady, Lydia; Jurga, Witold; Clérac, Rodolphe; Fourmigué, Marc

    2009-04-28

    The sulfiding of benzils with P(4)S(10) in 1,3-dimethyl-2-imidazolidinone (DMI) as solvent allows for a direct synthesis of neutral radical, gold dithiolene complexes based on 1,2-bis-(4-alkoxy-phenyl)ethylene-1,2-dithiolate ligands with n-butyl, n-octyl and n-dodecyl chains. The three neutral and soluble complexes Au-OC(4), Au-OC(8) and Au-OC(12) exhibit a near infrared (NIR) absorption band around 1.5 mum and EPR characteristics which confirm a strong delocalization of the spin density on the electron-rich dithiolene ligands. X-Ray crystal structures of Au-OC(4) and Au-OC(12) are compared with those of the corresponding nickel complexes. They are characterised by segregation of the alkyl chains into layered structures with a stacking of the radical complexes into alternated spin chains, confirmed by the temperature dependence of the magnetic susceptibility which attests for antiferromagnetic interactions and a singlet ground state. Observations under polarising microscope and DSC experiments do not reveal a thermotropic behaviour for Au-OC(12).

  13. Tris(pyrazolyl)phosphine oxide and Tris(triazolyl)phosphine oxide scorpion ligands

    NARCIS (Netherlands)

    Tazelaar, Cornelis G J; Lyaskovskyy, Volodymyr; Van Doorn, Ilana M.; Schaapkens, Xander; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jack; Lammertsma, Koop

    2014-01-01

    DFT calculations were performed on copper(I) complexes of neutral scorpion ligands based on either pyrazolyl (Pz) or triazolyl (Tz) rings with both methane and phosphine oxide apexes, that is, HC(Pz)3, OP(Pz)3, HC(Tz)3, and OP(Tz)3. The analyses reveal that all four ligands have similar donor proper

  14. Tris(pyrazolyl)phosphine oxide and Tris(triazolyl)phosphine oxide scorpion ligands

    NARCIS (Netherlands)

    Tazelaar, Cornelis G J; Lyaskovskyy, Volodymyr; Van Doorn, Ilana M.; Schaapkens, Xander; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jack; Lammertsma, Koop

    2014-01-01

    DFT calculations were performed on copper(I) complexes of neutral scorpion ligands based on either pyrazolyl (Pz) or triazolyl (Tz) rings with both methane and phosphine oxide apexes, that is, HC(Pz)3, OP(Pz)3, HC(Tz)3, and OP(Tz)3. The analyses reveal that all four ligands have similar donor proper

  15. The ligand redox behavior and role in 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene nickel-TMA(MAO) systems for ethylene polymerization.

    Science.gov (United States)

    Gao, Wei; Xin, Lan; Hao, Zhiqiang; Li, Guodong; Su, Ji-Hu; Zhou, Lijing; Mu, Ying

    2015-04-25

    The BIAN ligands in Brookhart catalysts were proved to be redox-active during the catalyst activation with alkylaluminum or MAO, and the neutral catalytically active species with a radical anionic BIAN rather than the cationic ones with a neutral BIAN ligand were confirmed to be formed in the catalytic system.

  16. Bleach Neutralizes Mold Allergens

    Science.gov (United States)

    Science Teacher, 2005

    2005-01-01

    Researchers at National Jewish Medical and Research Center have demonstrated that dilute bleach not only kills common household mold, but may also neutralize the mold allergens that cause most mold-related health complaints. The study, published in the Journal of Allergy and Clinical Immunology, is the first to test the effect on allergic…

  17. CO2-Neutral Fuels

    NARCIS (Netherlands)

    Goede, A.; van de Sanden, M. C. M.

    2016-01-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy

  18. CO2-Neutral Fuels

    Science.gov (United States)

    Goede, Adelbert; van de Sanden, Richard

    2016-06-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy efficiency.

  19. CO2-Neutral Fuels

    NARCIS (Netherlands)

    Goede, A.; van de Sanden, M. C. M.

    2016-01-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy

  20. Structure simulation into a lamellar supramolecular network and calculation of the metal ions/ligands ratio

    Directory of Open Access Journals (Sweden)

    Visa Aurelia

    2012-08-01

    Full Text Available Abstract Background Research interest in phosphonates metal organic frameworks (MOF has increased extremely in the last two decades, because of theirs fascinating and complex topology and structural flexibility. In this paper we present a mathematical model for ligand/metal ion ratio of an octahedral (Oh network of cobalt vinylphosphonate (Co(vP·H2O. Results A recurrent relationship of the ratio between the number of ligands and the number of metal ions in a lamellar octahedral (Oh network Co(vP·H2O, has been deducted by building the 3D network step by step using HyperChem 7.52 package. The mathematical relationship has been validated using X ray analysis, experimental thermogravimetric and elemental analysis data. Conclusions Based on deducted recurrence relationship, we can conclude prior to perform X ray analysis, that in the case of a thermogravimetric analysis pointing a ratio between the number of metal ions and ligands number around 1, the 3D network will have a central metal ion that corresponds to a single ligand. This relation is valid for every type of supramolecular network with divalent metal central ion Oh coordinated and bring valuable information with low effort and cost.

  1. Rh2 (S-1,2-NTTL)4 : A novel Rh2 (S-PTTL)4 analog with lower ligand symmetry for asymmetric synthesis of chiral cyclopropylphosphonates.

    Science.gov (United States)

    Adly, Frady G; Maddalena, Johncarlo; Ghanem, Ashraf

    2014-11-01

    A new series of dirhodium(II) tetracarboxylate was derived from N-1,2-naphthaloyl-(S)-amino acid ligands. In terms of enantioselectivity, Rh2 (S-1,2-NTTL)4 () derived from N-1,2-naphthaloyl-(S)-tert-leucine, was the best-performing catalyst among the new series in the enantioselective synthesis of cyclopropylphosphonate derivatives (up to >99% enantiomeric excess). A predictive model was proposed to justify the observed high enantiomeric induction exhibited by Rh2 (S-1,2-NTTL)4 with donor-acceptor phosphonate carbenoids.

  2. Luminescence study of europium(III) tris(β-diketonato)/phosphonate complexes in chloroform

    Institute of Scientific and Technical Information of China (English)

    Stefan Lis; Zbigniew Piskula; Krzysztof Staninski; Sayaka Tamaki; Masayuki Inoue; Yuko Hasegawa

    2008-01-01

    The extraction of Eu(III) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltrifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β of the first complexes between tris(β-diketonato)Eu(III) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(III) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(III), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(III) luminescence in the complexes as well as the observation of the extractability of Eu(III) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(III) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(III) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(III). It was not significant whether the donor atoms were N or O.

  3. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  4. Etching of Crystalline ZnO Surfaces upon Phosphonic Acid Adsorption: Guidelines for the Realization of Well-Engineered Functional Self-Assembled Monolayers.

    Science.gov (United States)

    Ostapenko, Alexandra; Klöffel, Tobias; Eußner, Jens; Harms, Klaus; Dehnen, Stefanie; Meyer, Bernd; Witte, Gregor

    2016-06-01

    Functionalization of metal oxides by means of covalently bound self-assembled monolayers (SAMs) offers a tailoring of surface electronic properties such as their work function and, in combination with its large charge carrier mobility, renders ZnO a promising conductive oxide for use as transparent electrode material in optoelectronic devices. In this study, we show that the formation of phosphonic acid-anchored SAMs on ZnO competes with an unwanted chemical side reaction, leading to the formation of surface precipitates and severe surface damage at prolonged immersion times of several days. Combining atomic force microscopy (AFM), X-ray diffraction (XRD), and thermal desorption spectroscopy (TDS), the stability and structure of the aggregates formed upon immersion of ZnO single crystal surfaces of different orientations [(0001̅), (0001), and (101̅0)] in phenylphosphonic acid (PPA) solution were studied. By intentionally increasing the immersion time to more than 1 week, large crystalline precipitates are formed, which are identified as zinc phosphonate. Moreover, the energetics and the reaction pathway of this transformation have been evaluated using density functional theory (DFT), showing that zinc phosphonate is thermodynamically more favorable than phosphonic acid SAMs on ZnO. Precipitation is also found for phosphonic acids with fluorinated aromatic backbones, while less precipitation occurs upon formation of SAMs with phenylphosphinic anchoring units. By contrast, no precipitates are formed when PPA monolayer films are prepared by sublimation under vacuum conditions, yielding smooth surfaces without noticeable etching.

  5. Adsorbed States of phosphonate derivatives of N-heterocyclic aromatic compounds, imidazole, thiazole, and pyridine on colloidal silver: comparison with a silver electrode.

    Science.gov (United States)

    Podstawka, Edyta; Olszewski, Tomasz K; Boduszek, Bogdan; Proniewicz, Leonard M

    2009-09-03

    Here, we report a systematic surface-enhanced Raman spectroscopy (SERS) study of the structures of phosphonate derivatives of the N-heterocyclic aromatic compounds imidazole (ImMeP ([hydroxy(1H-imidazol-5-yl)methyl]phosphonic acid) and (ImMe)(2)P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]phosphinic acid)), thiazole (BAThMeP (butylaminothiazol-2-yl-methyl)phosphonic acid) and BzAThMeP (benzylaminothiazol-2-yl-methyl)phosphonic acid)), and pyridine ((PyMe)(2)P (bis[(hydroxypyridin-3-yl-methyl)]phosphinic acid)) adsorbed on nanometer-sized colloidal particles. We compared these structures to those on a roughened silver electrode surface to determine the relationship between the adsorption strength and the geometry. For example, we showed that all of these biomolecules interact with the colloidal surface through aromatic rings. However, for BzAThMeP, a preferential interaction between the benzene ring and the colloidal silver surface is observed more so than that between the thiazole ring and this substrate. The PC(OH)C fragment does not take part in the adsorption process, and the phosphonate moiety of ImMeP and (ImMe)(2)P, being removed from the surface, only assists in this process.

  6. Adsorption of strontium (II) metal ions using phosphonate-functionalized polymer

    Indian Academy of Sciences (India)

    S M BHOSLE; S PONRATHNAM; S S TAMBE; N N CHAVAN

    2016-10-01

    Diethyl[3-(methoxydimethylsilyl)propyl]phosphonate (DMPP) polymer was synthesized for the strontium (II) metal ion recovery using diethylallylphosphonate as staring material. Diethylallylphosphonate was reactedwith poly(methylhydro)siloxane (MW 1900–2000 g mol$^{−1}$) in the presence of Speier’s catalyst. The synthesized monomer was characterized by IR, ${}^1$H NMR, ${}^{13}$C NMR and FT-IR spectroscopy techniques, and the synthesizedpolymers were characterized by IR and NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and solubility. The synthesized polymer was used for sequestering strontium metal from the aqueous solution. The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbentdose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, and pseudo-firstand second-order models. Results of this study indicate that the synthesized polymer DMPP has been effective inremoving Sr(II) from the aqueous solution.

  7. Adsorption of phosphonate antiscalant from reverse osmosis membrane concentrate onto granular ferric hydroxide.

    Science.gov (United States)

    Boels, Luciaan; Keesman, Karel J; Witkamp, Geert-Jan

    2012-09-04

    Adsorptive removal of antiscalants offers a promising way to improve current reverse osmosis (RO) concentrate treatment processes and enables the reuse of the antiscalant in the RO desalination process. This work investigates the adsorption and desorption of the phosphonate antiscalant nitrilotris(methylenephosphonic acid) (NTMP) from RO membrane concentrate onto granular ferric hydroxide (GFH), a material that consists predominantly of akaganéite. The kinetics of the adsorption of NTMP onto GFH was predicted fairly well with two models that consider either combined film-pore or combined film-surface diffusion as the main mechanism for mass transport. It is also demonstrated that NTMP is preferentially adsorbed over sulfate by GFH at pH 7.85. The presence of calcium causes a transformation in the equilibrium adsorption isotherm from a Langmuir type to a Freundlich type with much higher adsorption capacities. Furthermore, calcium also increases the rate of adsorption substantially. GFH is reusable after regeneration with sodium hydroxide solution, indicating that NTMP can be potentially recovered from the RO concentrate. This work shows that GFH is a promising adsorbent for the removal and recovery of NTMP antiscalant from RO membrane concentrates.

  8. Thermal and Dielectric Behavior Studies of Poly(Arylene Ether Sulfones with Sulfonated and Phosphonated Pendants

    Directory of Open Access Journals (Sweden)

    Shimoga D. Ganesh

    2016-01-01

    Full Text Available The present paper discusses the aspects of the synthesizing valeric acid based poly(ether sulfones with active carboxylic acid pendants (VALPSU from solution polymerization technique via nucleophilic displacement polycondensation reaction among 4,4′-dichlorodiphenyl sulfone (DCDPS and 4,4′-bis(4-hydroxyphenyl valeric acid (BHPA. The conditions necessary to synthesize and purify the polymer were investigated in some detail. The synthesized poly(ether sulfones comprise sulfone and ether linkages in addition to reactive carboxylic acid functionality; these active carboxylic acid functional groups were exploited to hold the phenyl sulphonic acid and phenyl phosphonic acid pendants. The phenyl sulphonic acid pendants in VALPSU were easily constructed by altering active carboxylic acid moieties by sulfanilic acid using N,N′-dicyclohexylcarbodiimide (DCC mediated mild synthetic route, whereas the latter one was built in two steps. Initially, polyphosphoric acid condensation with VALPSU by 4-bromoaniline and next straightforward palladium catalyzed synthetic route, in both of which acidic pendants are clenched by polymer backbone via amide linkage. Without impairing the primary polymeric backbone modified polymers were prepared by varying the stoichiometric ratios of respective combinations. All the polymers were physicochemically characterized and pressed into tablets; electrical contacts were established to study the dielectric properties. Finally, the influence of the acidic pendants on the dielectric properties was examined.

  9. Adsorption Behaviors and Mechanism of Macroporous Phosphonic Acid Resin for Gadolinium

    Institute of Scientific and Technical Information of China (English)

    吴香梅; 熊春华; 姚彩萍

    2004-01-01

    The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg·g-1resin and 296 mg·g-1resin at 298 K in Hac-NaAc medium at pH 5.6. Gd(Ⅲ)adsorbed on PAR can be reductively eluted by 0.5~5.0 mol·L-1 HCl used as eluant and the elution percentage is up to 94.7% in 1.0 mol·L-1 HCl. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k298=3.96×10-5 s-1. The adsorption behavior of PAR for Gd(Ⅲ) conforms to the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change △H of PAR for Gd(Ⅲ)is 22.6kJ·mol-1. The apparent adsorption activation energy(Ea)of PAR for Gd(Ⅲ)is 5.0 kJ·mol-1. The molar coordination ratio of the functional group of PAR to Gd(Ⅲ)is about 3∶1. The adsorption mechanism of PAR for Gd(Ⅲ)was examined by using chemical method and IR spectrometry.

  10. Studies on the Adsorption of Amino Methylene Phosphonic Acid Resin for Holmium(Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    吴香梅; 熊春华; 姚彩萍

    2003-01-01

    The adsorption behavior and mechanism of a novel chelate resin, amino methylene phosphonic acid resin (APAR) for Ho(Ⅲ) were investigated. The statically saturated adsorption capacity is 258 mg·g-1 resin at 298 K in Hac-NaAc medium. The Ho(Ⅲ) adsorbed on APAR can be repeatedly eluted by 3.0 mol·L-1 HCl and the elution percentage is as high as 95.8%. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k298=1.14×10-5 s-1. The adsorption behavior of APAR for Ho(Ⅲ) obeys the Freundlich isotherm. The ther modynamic adsorption parameter, enthalpy change ΔH of APAR for Ho(Ⅲ) is 11 .4 kJ·mol-1. The apparent activation energy is Ea=15.8 kJ·mol- 1. The molar coordination ratio of the functional group of APAR to Ho(Ⅲ) is a bout 2∶1. The adsorption mechanism of APAR for Ho(Ⅲ) was examined by using chemical method and IR spectrometry.

  11. Assembly of phosphonic acids on GaN and AlGaN

    Energy Technology Data Exchange (ETDEWEB)

    Simpkins, B S; Stine, R; Theodore, N D; Pehrsson, P E [Chemistry Division, Naval Research Laboratory, Washington DC (United States); Hong, S [Thomas Jefferson High School, McClean, VA (United States); Maekinen, A J [Optical Sciences Division, Naval Research Laboratory, Washington, DC (United States); Mastro, M A; Eddy, C R Jr [Electronics Science and Technology Division, Naval Research Laboratory, Washington, DC (United States)

    2010-01-13

    Self-assembled monolayers of octadecylphosphonic acid and 16-phosphonohexadecanoic acid (PHDA) were formed on the semiconductor substrates gallium nitride (GaN) and aluminium gallium nitride (AlGaN). The presence of the molecular layers was verified through x-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. Structural information was acquired with infrared spectroscopy which verified the bonding orientation of the carboxyl-containing PHDA. The impact of the molecular layers on the channel conductivity and the surface electronic structure of an AlGaN/GaN heterostructure was measured. Our results indicate that pinning of the surface Fermi level prohibits modification of the channel conductivity by the layer. However, a surface dipole of {approx}0.8 eV is present and associated with both phosphonic acid layers. These results are of direct relevance to field-effect-based biochemical sensors and metal-semiconductor contact formation for this system and provide a fundamental basis for further applications of GaN and AlGaN technology in the fields of biosensing and microelectronics.

  12. Adsorption Behavior and Mechanism of Macroporous Phosphonic Acid Resin for Lu3+

    Institute of Scientific and Technical Information of China (English)

    WANG Hui-jun; XIONG Chun-hua

    2006-01-01

    The article is based on a research on the adsorption behavior and adsorption mechanism of macroporous phosphonic acid resin (PAR) for Lu3+ and the influence of the medium's pH, adsorption temperature, adsorption time, etc on adsorbing Lu3 + . The best value of medium's pH to the adsorption of PAR for Lu3 + was found to be 4.92. The static adsorption maximum capacity of PAR for Lu3 + is 220 mg· g-1. The thermodynamic adsorption parameters are respectively △H= 11.3 kJ·mol-1, △S =46.3 J·mol-1 ·K-1, △G = - 2.50 kJ·mol-1 and the apparent activity energy is Ea= 31.4 kJ· mol- 1. The adsorption behavior of PAR for Lu3 + obeys the Freundlich isotherm. The apparent adsorption rate constant is k298 = 4.68 × 10-5 s-1. The coordinate ratio of the functional radical to Lu3 + is approximately 4: 1. The best eluant is 1.0 mol· L- 1 HCl. The adsorption mechanism of PAR for Lu3 + was separately confirmed by chemical analysis and IR spectra.

  13. Effects of radiation, acid, and base on the extractant dihexyl-(diethylcarbamoyl)methyl) phosphonate

    Energy Technology Data Exchange (ETDEWEB)

    Bahner, C.T.; Shoun, R.R.; McDowell, W.J.

    1981-11-01

    The effects of exposure to gamma radiation (/sup 60/Co) and of contact with acidic and basic aqueous solutions on dihexyl((diethylcarbamoyl)methyl)phosphonate (DHDECMP) were studied. Gamma radiation decomposes DHDECMP into a variety of products. The most troublesome of those are the acidic compounds that cause problems in stripping the actinides and lanthanides from the extractant at low acid concentrations. The rate of degradation of DHDECMP by radiation is about the same or only slightly higher than that of tri-n-butyl phosphate (TBP). It is relatively easy to remove the radiation-produced impurities by equilibration (scrubbing) with sodium carbonate or sodium hydroxide or by column chromatographic methods. The hydrolysis of DHDECMP in contact with aqueous solutions containing less than 3 M HNO/sub 3/ is not more severe than that of TBP under the same conditions but is significant above that acid concentration. Hydrolysis of DHDECMP in contact with aqueous sodium hydroxide solution does occur, but it should not pose an important problem with the short contact times such as those anticipated for the removal of the radiation-induced degradation products by caustic scrubbing. Results of various chromatographic tests to characterize the degradation products of DHDECMP are also given.

  14. Ultracold Neutral Plasmas

    CERN Document Server

    Killian, T C; Gupta, P; Laha, S; Martinez, Y N; Mickelson, P G; Nagel, S B; Saenz, A D; Simien, C E; Killian, Thomas C.

    2005-01-01

    Ultracold neutral plasmas are formed by photoionizing laser-cooled atoms near the ionization threshold. Through the application of atomic physics techniques and diagnostics, these experiments stretch the boundaries of traditional neutral plasma physics. The electron temperature in these plasmas ranges from 1-1000 K and the ion temperature is around 1 K. The density can approach $10^{11}$ cm$^{-3}$. Fundamental interest stems from the possibility of creating strongly-coupled plasmas, but recombination, collective modes, and thermalization in these systems have also been studied. Optical absorption images of a strontium plasma, using the Sr$^+$ ${^2S_{1/2}} -> {^2P_{1/2}}$ transition at 422 nm, depict the density profile of the plasma, and probe kinetics on a 50 ns time-scale. The Doppler-broadened ion absorption spectrum measures the ion velocity distribution, which gives an accurate measure of the ion dynamics in the first microsecond after photoionization.

  15. Between detection and neutralization.

    Energy Technology Data Exchange (ETDEWEB)

    Snell, Mark Kamerer; Green, Mary Wilson; Adams, Douglas Glenn; Pritchard, Daniel Allison

    2005-08-01

    Security system analytical performance analysis is generally based on the probability of system effectiveness. The probability of effectiveness is a function of the probabilities of interruption and neutralization. Interruption occurs if the response forces are notified in sufficient time to engage the adversary. Neutralization occurs if the adversary attack is defeated after the security forces have actively engaged the adversary. Both depend upon communications of data. This paper explores details of embedded communications functions that are often assumed to be inconsequential. It is the intent of the authors to bring focus to an issue in security system modeling that, if not well understood, has the potential to be a deciding factor in the overall system failure or effectiveness.

  16. Gargamelle: neutral current event

    CERN Multimedia

    1973-01-01

    This event shows real tracks of particles from the 1200 litre Gargamelle bubble chamber that ran on the PS from 1970 to 1976 and on the SPS from 1976 to 1979. In this image a neutrino passes close to a nucleon and reemerges as a neutrino. Such events are called neutral curent, as they are mediated by the Z0 boson which has no electric charge.

  17. Neutral atom traps.

    Energy Technology Data Exchange (ETDEWEB)

    Pack, Michael Vern

    2008-12-01

    This report describes progress in designing a neutral atom trap capable of trapping sub millikelvin atom in a magnetic trap and shuttling the atoms across the atom chip from a collection area to an optical cavity. The numerical simulation and atom chip design are discussed. Also, discussed are preliminary calculations of quantum noise sources in Kerr nonlinear optics measurements based on electromagnetically induced transparency. These types of measurements may be important for quantum nondemolition measurements at the few photon limit.

  18. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B. [Pacific Northwest Lab., Richland, WA (United States)

    1996-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used tin applications for the cost-effective removal of specific radionuclides from nuclear waste streams.

  19. Ultracold neutral plasmas

    Science.gov (United States)

    Lyon, M.; Rolston, S. L.

    2017-01-01

    By photoionizing samples of laser-cooled atoms with laser light tuned just above the ionization limit, plasmas can be created with electron and ion temperatures below 10 K. These ultracold neutral plasmas have extended the temperature bounds of plasma physics by two orders of magnitude. Table-top experiments, using many of the tools from atomic physics, allow for the study of plasma phenomena in this new regime with independent control over the density and temperature of the plasma through the excitation process. Characteristic of these systems is an inhomogeneous density profile, inherited from the density distribution of the laser-cooled neutral atom sample. Most work has dealt with unconfined plasmas in vacuum, which expand outward at velocities of order 100 m/s, governed by electron pressure, and with lifetimes of order 100 μs, limited by stray electric fields. Using detection of charged particles and optical detection techniques, a wide variety of properties and phenomena have been observed, including expansion dynamics, collective excitations in both the electrons and ions, and collisional properties. Through three-body recombination collisions, the plasmas rapidly form Rydberg atoms, and clouds of cold Rydberg atoms have been observed to spontaneously avalanche ionize to form plasmas. Of particular interest is the possibility of the formation of strongly coupled plasmas, where Coulomb forces dominate thermal motion and correlations become important. The strongest impediment to strong coupling is disorder-induced heating, a process in which Coulomb energy from an initially disordered sample is converted into thermal energy. This restricts electrons to a weakly coupled regime and leaves the ions barely within the strongly coupled regime. This review will give an overview of the field of ultracold neutral plasmas, from its inception in 1999 to current work, including efforts to increase strong coupling and effects on plasma properties due to strong coupling.

  20. The Weak Neutral Current

    CERN Document Server

    Erler, Jens

    2013-01-01

    This is a review of electroweak precision physics with particular emphasis on low-energy precision measurements in the neutral current sector of the electroweak theory and includes future experimental prospects and the theoretical challenges one faces to interpret these observables. Within the minimal Standard Model they serve as determinations of the weak mixing angle which are competitive with and complementary to those obtained near the Z-resonance. In the context of new physics beyond the Standard Model these measurements are crucial to discriminate between models and to reduce the allowed parameter space within a given model. We illustrate this for the minimal supersymmetric Standard Model with or without R-parity.

  1. Mod en neutral seksualitet!

    DEFF Research Database (Denmark)

    Leer, Jonatan

    2013-01-01

    the paradigm”. This notion was presented at a series of lectures at Collège de France in 1977. Through a reading of Barthes’s autobiography, Roland Barthes par Roland Barthes (1975), the article demonstrates how Barthes in this text tries to outplay the paradigms that rules over the hegemonic understanding...... of gender and sexuality; also the fragmented text presents a vision of a sexual utopia, a neutral sexuality, that tries – like the queer theory – to go and think beyond a binary conception of gender and sexuality. Finally, it is suggested that we should start to think about a movement of “French queer...

  2. Effect of time and deposition method on quality of phosphonic acid modifier self-assembled monolayers on indium zinc oxide

    Science.gov (United States)

    Sang, Lingzi; Knesting, Kristina M.; Bulusu, Anuradha; Sigdel, Ajaya K.; Giordano, Anthony J.; Marder, Seth R.; Berry, Joseph J.; Graham, Samuel; Ginger, David S.; Pemberton, Jeanne E.

    2016-12-01

    Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F5BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after ∼48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F13-octylphosphonic acid (F13OPA), and pentafluorinated benzyl phosphonic acid (F5BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48-168 h solution deposition at both room temperature and 70 °C result in contamination- and surface etch-free close-packed monolayers with good reproducibility. SAMs fabricated by micro-contact printing and spray coating are much less well ordered.

  3. Effect of Time and Deposition Method on Quality of Phosphonic Acid Modifier Self-Assembled Monolayers on Indium Zinc Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Sang, Lingzi; Knesting, Kristina M.; Bulusu, Anuradha; Sigdel, Ajaya K.; Giordano, Anthony J.; Marder, Seth R.; Berry, Joseph J.; Graham, Samuel; Ginger, David S.; Pemberton, Jeanne E.

    2016-12-15

    Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F5BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after -48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F13-octylphosphonic acid (F13OPA), and pentafluorinated benzyl phosphonic acid (F5BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48-168 h solution deposition at both room temperature and 70 degrees C result in contamination- and surface etch-free close-packed monolayers with good reproducibility. SAMs fabricated by micro-contact printing and spray coating are much less well ordered.

  4. Sol-gel synthesis of tantalum oxide and phosphonic acid-modified carbon nanotubes composite coatings on titanium surfaces.

    Science.gov (United States)

    Maho, Anthony; Detriche, Simon; Delhalle, Joseph; Mekhalif, Zineb

    2013-07-01

    Carbon nanotubes used as fillers in composite materials are more and more appreciated for the outstanding range of accessible properties and functionalities they generate in numerous domains of nanotechnologies. In the framework of biological and medical sciences, and particularly for orthopedic applications and devices (prostheses, implants, surgical instruments, …), titanium substrates covered by tantalum oxide/carbon nanotube composite coatings have proved to constitute interesting and successful platforms for the conception of solid and biocompatible biomaterials inducing the osseous regeneration processes (hydroxyapatite growth, osteoblasts attachment). This paper describes an original strategy for the conception of resistant and homogeneous tantalum oxide/carbon nanotubes layers on titanium through the introduction of carbon nanotubes functionalized by phosphonic acid moieties (-P(=O)(OH)2). Strong covalent C-P bonds are specifically inserted on their external sidewalls with a ratio of two phosphonic groups per anchoring point. Experimental results highlight the stronger "tantalum capture agent" effect of phosphonic-modified nanotubes during the sol-gel formation process of the deposits compared to nanotubes bearing oxidized functions (-OH, -C=O, -C(=O)OH). Particular attention is also paid to the relative impact of the rate of functionalization and the dispersion degree of the carbon nanotubes in the coatings, as well as their wrapping level by the tantalum oxide matrix material. The resulting effect on the in vitro growth of hydroxyapatite is also evaluated to confirm the primary osseous bioactivity of those materials. Chemical, structural and morphological features of the different composite deposits described herein are assessed by X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission (TEM) electronic microscopies, energy dispersive X-rays analysis (EDX) and peeling tests.

  5. Nucleoside-O-Methyl-(H)-Phosphinates: Novel Monomers for the Synthesis of Methylphosphonate Oligonucleotides Using H-Phosphonate Chemistry.

    Science.gov (United States)

    Kostov, Ondřej; Páv, Ondřej; Rosenberg, Ivan

    2017-09-18

    This unit comprises the straightforward synthesis of protected 2'-deoxyribonucleoside-O-methyl-(H)-phosphinates in both 3'- and 5'-series. These compounds represent a new class of monomers compatible with the solid-phase synthesis of oligonucleotides using H-phosphonate chemistry and are suitable for the preparation of both 3'- and 5'-O-methylphosphonate oligonucleotides. The synthesis of 4-toluenesulfonyloxymethyl-(H)-phosphinic acid as a new reagent for the preparation of O-methyl-(H)-phosphinic acid derivatives is described. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  6. Corrosion inhibition of low phosphonic multipolymer water treatment agent of industry circulating on brass in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In response to environmental guidelines, a low phosphonic multipolymer was synthesized and its corrosion inhibition efficiency to brass in synthetic water was investigated through weight loss measurements and electrochemical tests.It showed that the synthesized inhibitor decreased corrosion under the conditions tested.Potentiodynamic polarization curves indicated that the new inhibitor acted as an anodic inhibitor, reducing metal dissolution.The composition of protective films formed on the brass was studied by energy-dispersive X-ray analysis (EDX).The inhibition effects were due to the formation of a protective film of the multipolymer inhibitor on the metal surface.

  7. Transcriptional and cellular responses of the green alga Chlamydomonas reinhardtii to perfluoroalkyl phosphonic acids.

    Science.gov (United States)

    Sanchez, David; Houde, Magali; Douville, Mélanie; De Silva, Amila O; Spencer, Christine; Verreault, Jonathan

    2015-03-01

    Perfluoroalkyl phosphonic acids (PFPAs), a new class of perfluoroalkyl substances used primarily in the industrial sector as surfactants, were recently detected in surface water and wastewater treatment plant effluents. Toxicological effects of PFPAs have as yet not been investigated in aquatic organisms. The objective of the present study was to evaluate the effects of perfluorooctylphosphonic acid (C8-PFPA) and perfluorodecylphosphonic acid (C10-PFPA) exposure (31-250μg/L) on Chlamydomonas reinhardtii using genomic (qRT-PCR), biochemical (reactive oxygen species production (ROS) and lipid peroxidation), and physiological (cellular viability) indicators. After 72h of exposure, no differences were observed in cellular viability for any of the two perfluorochemicals. However, increase in ROS concentrations (36% and 25.6% at 125 and 250μg/L, respectively) and lipid peroxidation (35.5% and 35.7% at 125 and 250μg/L, respectively) was observed following exposure to C10-PFPA. C8-PFPA exposure did not impact ROS production and lipid peroxidation in algae. To get insights into the molecular response and modes of action of PFPA toxicity, qRT-PCR-based assays were performed to analyze the transcription of genes related to antioxidant responses including superoxide dismutase (SOD-1), glutathione peroxidase (GPX), catalase (CAT), glutathione S-transferase (GST), and ascorbate peroxidase (APX I). Genomic analyses revealed that the transcription of CAT and APX I was up-regulated for all the C10-PFPA concentrations. In addition, PFPAs were quantified in St. Lawrence River surface water samples and detected at concentrations ranging from 250 to 850pg/L for C8-PFPA and 380 to 650pg/L for C10-PFPA. This study supports the prevalence of PFPAs in the aquatic environment and suggests potential impacts of PFPA exposure on the antioxidant defensive system in C. reinhardtii. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

  8. Samarium-153 ethylenediamine tetramethylene phosphonate therapy for bone pain palliation in skeletal metastases

    Directory of Open Access Journals (Sweden)

    Tripathi Madhavi

    2006-01-01

    Full Text Available BACKGROUND: Systemic therapy with radionuclides may be used for the treatment of patients with painful skeletal metastases owing to its efficacy, low cost and low toxicity. Imported radionuclides for pain palliation, like Strontium-89 are expensive; particularly for developing countries. In the Indian scenario, Samarium-153 (Sm-153 is produced in our own reactors and as a result, it is readily available and economical. AIM: We undertook this study to determine the efficacy and toxicity of single-dose Sm-153 ethylenediamine tetramethylene phosphonate as a palliative treatment for painful skeletal metastases. MATERIALS AND METHODS: Eightysix patients with painful skeletal metastases from various primaries, were treated with Sm-153 EDTMP at a dose of 37 MBq/kg. The effects were evaluated according to change in visual analogue pain score, analgesic consumption, Karnofsky performance score, mobility score and blood count tests, conducted regularly for 16 weeks. STATISTICS: Repeated measures analysis. RESULTS: The overall response rates were 73%, while complete response was seen in 12.4%. Reduction in analgesic consumption with improvement in Karnofsky performance score and mobility score, was seen in all responders. Response rates were 80.3 and 80.5% in breast and prostate cancer, respectively. One case, each of Wilms tumor, ovarian cancer, germ cell tumor testis, multiple myeloma, primitive neuroectodermal tumor and oesophageal cancer, did not respond to therapy. No serious side-effects were noted, except for fall in white blood cell, platelet and haemoglobin counts, which gradually returned to normal levels by six-eight weeks. CONCLUSION: Sm-153 EDTMP provided effective palliation in 73% patients with painful bone metastases: the major toxicity was temporary myelosuppression.

  9. The Fungicide Phosphonate Disrupts the Phosphate-Starvation Response in Brassica nigra Seedlings.

    Science.gov (United States)

    Carswell, C.; Grant, B. R.; Theodorou, M. E.; Harris, J.; Niere, J. O.; Plaxton, W. C.

    1996-01-01

    The development of Brassica nigra seedlings over 20 d of growth was disrupted by the fungicide phosphonate (Phi) in a manner inversely correlated with nutritional inorganic phosphate (Pi) levels. The growth of Pi-sufficient (1.25 mM Pi) seedlings was suppressed when 10, but not 5, mM Phi was added to the nutrient medium. In contrast, the fresh weights and root:shoot ratios of Pi-limited (0.15 mM) seedlings were significantly reduced at 1.5 mM Phi, and they progressively declined to about 40% of control values as medium Phi concentration was increased to 10 mM. Intracellular Pi levels generally decreased in Phi-treated seedlings, and Phi accumulated in leaves and roots to levels up to 6- and 16-fold that of Pi in Pi-sufficient and Pi-limited plants, respectively. Extractable activities of the Pi-starvation-inducible enzymes phosphoenolpyruvate phosphatase and inorganic pyrophosphate-dependent phosphofructokinase were unaltered in Pi-sufficient seedlings grown on 5 or 10 mM Phi. However, when Pi-limited seedlings were grown on 1.5 to 10 mM Phi (a) the induction of phosphoenolpyruvate phosphatase and inorganic pyrophosphate-dependent phosphofructokinase activities by Pi limitation was reduced by 40 to 90%, whereas (b) soluble protein concentrations and the activities of the ATP-dependent phosphofructokinase and pyruvate kinase were unaffacted. It is concluded that Phi specifically interrupts processes involved in regulation of the Pi-starvation response in B. nigra.

  10. Rapid Synthesis and Antiviral Activity of (Quinazolin-4-YlaminoMethyl-Phosphonates Through Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Baoan Song

    2012-06-01

    Full Text Available This study describes the simple synthesis of new (quinazolin-4-ylamino methylphosphonates via microwave irradiation. Substituted-2-aminobenzonitrile reacted with 1,1-dimethoxy-N,N-dimethylmethanamine at a reflux condition to obtain N'-(substituted-2-cyanophenyl-N,N-dimethylformamidine (1. The subsequent reaction of this intermediate product with α-aminophosphonate (2 in a solution containing glacial acetic acid in 2-propanol through microwave irradiation resulted in the formation of (quinazolin-4-ylaminomethyl-phosphonate derivatives 3a to 3x, which were unequivocally characterized by the spectral data and elemental analysis. The influence of the reaction conditions on the yield of 3a was investigated to optimize the synthetic conditions. The relative optimal conditions for the synthesis of 3a include a 1:1 molar ratio of N’-(2-cyanophenyl-N,N-dimethylformamidine to diethyl amino(phenylmethylphosphonate and a 4:1 volume ratio of isopropanol to HOAc in the solvent mixture, at a reaction temperature of 150 °C, with a microwave power of 100 W and a corresponding pressure of 150 psi for 20 min in the microwave synthesizer. The yield of 3a was approximately 79%, whereas those of 3b to 3x were approximately 77% to 86%. Some of the synthesized compounds displayed weak to good anti-Tobacco mosaic virus (TMV activity.

  11. Is /h/ phonetically neutral?

    Science.gov (United States)

    Robb, Michael P; Chen, Yang

    2009-11-01

    Use of /h/ in the phrase, 'Say /hVC/ again' has been tacitly assumed to provide a neutral phonetic context in which to study the articulatory characteristics of speech either preceding or following /h/ articulation. Yet, assessment of the stability or neutrality of /h/ has gone untested. The current study sought to determine whether articulation of /h/ differs according to sex and language accent, as well as to examine its influence on subsequent vowel articulation. Selected acoustic features of /hVC/ were measured in 40 speakers of American English (AE) and 40 speakers of Mandarin-accented English (MAE). Results of an analysis of /h/ duration revealed no sex differences within each language group, however considerable variation was found according to accented vs unaccented English. Clear sex differences were found for the production of /h/, occurring more often among male speakers regardless of language variety. Considerable variation in production of /h/ was found between language groups. Analysis of vowel formant frequencies immediately following /h/ articulation indicated minimal coarticulatory effects for both AE and MAE speakers. The present results appear to support the suggestion that /h/ is not exclusively sex-linked and may indeed vary according to non-biological factors. In spite of these variations, /h/ articulation appears to have a negligible influence on neighbouring vowel articulation.

  12. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    Science.gov (United States)

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  13. Organic neutralization agents for neutralization-reionization mass spectrometry.

    Science.gov (United States)

    Zhang, M Y; McLafferty, F W

    1992-02-01

    Porter has shown that excited neutrals of specified internal energies can be prepared by neutralization of an ion beam with metal vapors of low ionization potential (IP). For specific problems in neutralization-reionization mass spectrometry, a metal with the desired IP value may not be available, or it may present experimental problems such as a high vaporization temperature, instrument contamination, or detector instability. The use of organic neutralization agents such as tetra-p-anisylethylene (IP = 6.0 eV) can minimize these problems (although cross sections for neutralization with these are a factor of 5 lower than those with metals), and can provide a much wider range of IP values. Their utility is demonstrated in the neutralization of C4H4 (+•) and CH8 (+•) ions to produce C4H4 and C4H8 of selected internal energies. However, for CH4 (+•) neutralization, the CH4 neutrals formed have a much lower internal energy than predicted, indicating that electron transfer from the neutralization agent predominantly produces its ions in excited states.

  14. Spectroscopy of neutral radium

    Energy Technology Data Exchange (ETDEWEB)

    Mol, Aran; De, Subhadeep; Jungmann, Klaus; Wilschut, Hans; Willmann, Lorenz [KVI, University of Groningen, Groningen (Netherlands)

    2008-07-01

    The heavy alkaline earth atoms radium is uniquely sensitive towards parity and time reversal symmetry violations due to a large enhancement of an intrinsic permanent electric dipole moment of the nucleous or the electron. Furthermore, radium is sensitive to atomic parity violation and the nuclear anapole moment. To prepare such experiments spectroscopy of relevant atomic states need to be done. At a later stage we will build a neutral atom trap for radium. We have built an atomic beam of the short lived isotope {sup 225}Ra with a flux of several 10{sup 4} atoms/sec. We are preparing the laser spectroscopy using this beam setup. In the preparation for efficient laser cooling and trapping we have successfully trapped barium, which is similar in it's requirements for laser cooling. The techniques which we have developed with barium can be used to trap rare radium isotopes. We report on the progress of the experiments.

  15. Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Somov, N. V., E-mail: somov@phys.unn.ru [University of Nizhni Novgorod (Russian Federation); Chausov, F. F., E-mail: chaus@uni.udm.ru [Udmurt State University (Russian Federation)

    2015-03-15

    Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å, c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.

  16. Synthesis of highly phosphonic acid functionalized benzene-bridged periodic mesoporous organosilicas for use as efficient dye adsorbents.

    Science.gov (United States)

    Deka, Juti Rani; Liu, Chia-Ling; Wang, Tzu-Hua; Chang, Wei-Chieh; Kao, Hsien-Ming

    2014-08-15

    Periodic mesoporous organosilicas (PMOs) with benzene bridging groups in the silica wall were functionalized with a tunable content of phosphonic acid groups. These bifunctional materials were synthesized by co-condensation of two different organosilane precursors, that is, 1,4-bis(triethoxysilyl)benzene (BTEB) and sodium 3-(trihydroxysilyl)propyl methyl phosphate (SPMP), under acidic conditions using nonionic surfactant Brij-S10 as template. The materials exhibited well-ordered mesostructures and were characterized by X-ray diffraction, nitrogen sorption, TEM, TGA, FTIR, and solid-state NMR measurements. The materials thus obtained were employed as adsorbents to remove different types of dyes, for example, cationic dyes methylene blue and phenosafranine, anionic orange II, and amphoteric rhodamine B, from aqueous solutions. The materials exhibited a remarkably high adsorption capacity than activated carbon due to their ordered mesostructures, a large number of phosphonic acid groups, and high surface areas. The adsorption was mainly governed by electrostatic interaction, but also involved π-π stacking interaction as well as hydrogen bonding. The adsorption kinetics can be better fitted by the pseudo-second order model. The adsorption process was controlled by the mechanisms of external mass transfer and intraparticle diffusion. The materials retained more than 97% dye removal efficiency after use for five consecutive cycles.

  17. Relative binding affinity of carboxylate-, phosphonate-, and bisphosphonate-functionalized gold nanoparticles targeted to damaged bone tissue

    Energy Technology Data Exchange (ETDEWEB)

    Ross, Ryan D. [Rush University Medical Center, Department of Anatomy and Cell Biology (United States); Cole, Lisa E.; Roeder, Ryan K., E-mail: rroeder@nd.edu [University of Notre Dame, Department of Aerospace and Mechanical Engineering Bioengineering Graduate Program (United States)

    2012-10-15

    Functionalized Au NPs have received considerable recent interest for targeting and labeling cells and tissues. Damaged bone tissue can be targeted by functionalizing Au NPs with molecules exhibiting affinity for calcium. Therefore, the relative binding affinity of Au NPs surface functionalized with either carboxylate (l-glutamic acid), phosphonate (2-aminoethylphosphonic acid), or bisphosphonate (alendronate) was investigated for targeted labeling of damaged bone tissue in vitro. Targeted labeling of damaged bone tissue was qualitatively verified by visual observation and backscattered electron microscopy, and quantitatively measured by the surface density of Au NPs using field-emission scanning electron microscopy. The surface density of functionalized Au NPs was significantly greater within damaged tissue compared to undamaged tissue for each functional group. Bisphosphonate-functionalized Au NPs exhibited a greater surface density labeling damaged tissue compared to glutamic acid- and phosphonic acid-functionalized Au NPs, which was consistent with the results of previous work comparing the binding affinity of the same functionalized Au NPs to synthetic hydroxyapatite crystals. Targeted labeling was enabled not only by the functional groups but also by the colloidal stability in solution. Functionalized Au NPs were stabilized by the presence of the functional groups, and were shown to remain well dispersed in ionic (phosphate buffered saline) and serum (fetal bovine serum) solutions for up to 1 week. Therefore, the results of this study suggest that bisphosphonate-functionalized Au NPs have potential for targeted delivery to damaged bone tissue in vitro and provide motivation for in vivo investigation.

  18. Neutral Evolution of Mutational Robustness

    CERN Document Server

    Van Nimwegen, E; Huynen, M; Nimwegen, Erik van; Crutchfield, James P.; Huynen, Martijn

    1999-01-01

    We introduce and analyze a general model of a population evolving over a network of selectively neutral genotypes. We show that the population's limit distribution on the neutral network is solely determined by the network topology and given by the principal eigenvector of the network's adjacency matrix. Moreover, the average number of neutral mutant neighbors per individual is given by the matrix spectral radius. This quantifies the extent to which populations evolve mutational robustness: the insensitivity of the phenotype to mutations. Since the average neutrality is independent of evolutionary parameters---such as, mutation rate, population size, and selective advantage---one can infer global statistics of neutral network topology using simple population data available from {\\it in vitro} or {\\it in vivo} evolution. Populations evolving on neutral networks of RNA secondary structures show excellent agreement with our theoretical predictions.

  19. Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Olivares, Astrid M.; Hill, David E.; Laskin, Julia

    2015-01-01

    We present a systematic study of the effect of the number of methyl (Me) and cyclohexyl (Cy) functional groups in monodentate phosphine ligands on the solution-phase synthesis of ligated sub-nanometer gold clusters and their gas-phase fragmentation pathways. Small mixed ligand cationic gold clusters were synthesized using ligand exchange reactions between pre-formed triphenylphosphine ligated (PPh3) gold clusters and monodentate Me- and Cy-substituted ligands in solution and characterized using electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation (CID) experiments. Under the same experimental conditions, larger gold-PPh3 clusters undergo efficient exchange of unsubstituted PPh3 ligands for singly Me- and Cy-substituted PPh2Me and PPh2Cy ligands. The efficiency of ligand exchange decreases with an increasing number of Me or Cy groups in the substituted phosphine ligands. CID experiments performed for a series of ligand-exchanged gold clusters indicate that loss of a neutral Me-substituted ligand is preferred over loss of a neutral PPh¬3 ligand while the opposite trend is observed for Cy-substituted ligands. The branching ratio of the competing ligand loss channels is strongly correlated with the electron donating ability of the phosphorous lone pair as determined by the relative proton affinity of the ligand. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3< PPh2Cy < PPhCy2< PCy3. Furthermore, the difference in relative ligand binding energies increases with the number of substituted PPh3-mMem or PPh3-mCym ligands (L) exchanged onto each cluster. This study provides the first experimental determination of the relative binding energies of ligated gold clusters containing differently substituted monophosphine ligands, which are important to controlling their synthesis and reactivity in solution. The results also indicate that ligand substitution is an important

  20. Hydroxyiminodisuccinic acid (HIDS): A novel biodegradable chelating ligand for the increase of iron bioavailability and arsenic phytoextraction

    OpenAIRE

    Rahman, M. Azizur; Hasegawa, Hiroshi; Kadohashi, K.; Maki, Teruya; Ueda, Kazumasa

    2009-01-01

    The influence of biodegradable chelating ligands on arsenic and iron uptake by hydroponically grown rice seedlings (Oryza sativa L.) was investigated. Even though the growth solution contained sufficient Fe, the growth of rice seedlings gradually decreased up to 76% with the increase of pH of the solution from 7 to 11. Iron forms insoluble ferric hydroxide complexes at neutral or alkaline pH in oxic condition. Chelating ligands produce soluble 'Fe-ligand complex' which assist Fe uptake in pla...

  1. Strange neutral currents in nuclei

    CERN Document Server

    Ressell, M T; Aufderheide, M B; Bloom, S D; Resler, D A

    1995-01-01

    We examine the effects on the nuclear neutral current Gamow-Teller (GT) strength of a finite contribution from a polarized strange quark sea. We perform nuclear shell model calculations of the neutral current GT strength for a number of nuclei likely to be present during stellar core collapse. We compare the GT strength when a finite strange quark contribution is included to the strength without such a contribution. As an example, the process of neutral current nuclear de-excitation via \

  2. Ligand fitting with CCP4

    Science.gov (United States)

    2017-01-01

    Crystal structures of protein–ligand complexes are often used to infer biology and inform structure-based drug discovery. Hence, it is important to build accurate, reliable models of ligands that give confidence in the interpretation of the respective protein–ligand complex. This paper discusses key stages in the ligand-fitting process, including ligand binding-site identification, ligand description and conformer generation, ligand fitting, refinement and subsequent validation. The CCP4 suite contains a number of software tools that facilitate this task: AceDRG for the creation of ligand descriptions and conformers, Lidia and JLigand for two-dimensional and three-dimensional ligand editing and visual analysis, Coot for density interpretation, ligand fitting, analysis and validation, and REFMAC5 for macromolecular refinement. In addition to recent advancements in automatic carbohydrate building in Coot (LO/Carb) and ligand-validation tools (FLEV), the release of the CCP4i2 GUI provides an integrated solution that streamlines the ligand-fitting workflow, seamlessly passing results from one program to the next. The ligand-fitting process is illustrated using instructive practical examples, including problematic cases such as post-translational modifications, highlighting the need for careful analysis and rigorous validation. PMID:28177312

  3. Constraining the Europa Neutral Torus

    Science.gov (United States)

    Smith, Howard T.; Mitchell, Donald; mauk, Barry; Johnson, Robert E.; clark, george

    2016-10-01

    "Neutral tori" consist of neutral particles that usually co-orbit along with their source forming a toroidal (or partial toroidal) feature around the planet. The distribution and composition of these features can often provide important, if not unique, insight into magnetospheric particles sources, mechanisms and dynamics. However, these features can often be difficult to directly detect. One innovative method for detecting neutral tori is by observing Energetic Neutral Atoms (ENAs) that are generally considered produced as a result of charge exchange interactions between charged and neutral particles.Mauk et al. (2003) reported the detection of a Europa neutral particle torus using ENA observations. The presence of a Europa torus has extremely large implications for upcoming missions to Jupiter as well as understanding possible activity at this moon and providing critical insight into what lies beneath the surface of this icy ocean world. However, ENAs can also be produced as a result of charge exchange interactions between two ionized particles and in that case cannot be used to infer the presence of neutral particle population. Thus, a detailed examination of all possible source interactions must be considered before one can confirm that likely original source population of these ENA images is actually a Europa neutral particle torus. For this talk, we examine the viability that the Mauk et al. (2003) observations were actually generated from a neutral torus emanating from Europa as opposed to charge particle interactions with plasma originating from Io. These results help constrain such a torus as well as Europa source processes.

  4. Dual action of phosphonate herbicides in plants affected by herbivore--model study on black bean aphid Aphis fabae rearing on broad bean Vicia faba plants.

    Science.gov (United States)

    Lipok, Jacek

    2009-09-01

    The interactions between plants, herbicides and herbivore insects were studied as an aspect of possible side effect of the using of phosphonate herbicides. The experimental system was composed of phosphonate herbicides, broad bean Vicia faba (L.) plants and black bean aphid Aphis fabae (Scopoli). Two means of herbicide application, namely standard spraying and direct introduction of the herbicide into stem via glass capillary, were examined. The results obtained for N-2-piridylaminomethylene bisphosphonic acid and its derivatives show 10 times higher inhibition of the plant growth if glass capillary mode was used. When plants were infested by aphids 24h after the use of herbicide, a significant decrease in plant growth rate was observed in relation to plants treated with herbicides alone. Moreover, the sensitivity of aphids towards glyphosate, N-2-piridylaminomethylene bisphosphonic acid and its 3-methyl derivative introduced to artificial diet indicated that these herbicidal phosphonates possessed also insecticidal activity if applied in a systemic manner. Additionally, olfactometer measurements revealed that aphids preferred intact V. faba leaves over those that had been treated with sublethal doses of herbicides. The results achieved in these experiments indicate that the use of phosphonate herbicides decreases plant resistance and influences the number of aphids accompanied with treated plants. Regarding these facts it can be concluded that the combined effect of herbicide-induced stress and insect herbivory reduced plant fitness and thus should be considered as also a factor enabling the reduction of herbicide doses.

  5. A comparative analysis of pharmacokinetics properties of diagnostic bone-seeking radiopharmaceuticals on the basis of phosphonic acids and technetium-99m

    Science.gov (United States)

    Tishchenko, V. K.; Petriev, V. M.; Smoryzanova, O. A.; Zavestovskaya, I. N.

    2017-01-01

    This work is devoted to comparative research of pharmacokinetics properties of four bone-seeking radiopharmaceuticals (RPP) on the basis of bi- tetra- and penta-phosphonic acids. Biodistribution studies were performed in intact rats after intravenous injections of 99mTc-hydroxyethylidenediphosphonic acid (99mTc-HEDP), 99mTc-oxabiphor (99mTc-OXB), 99mTc-ethylenediaminetetramethylenephosphonic acid (99mTc-EDTMP) or 99mTc-diethylenetriaminopentakis(methylphosphonic acid) (99mTc-PPA). In the structure of the HEDP contains two phosphonic groups, OENTMP and EDTMP – four phosphonic groups, PPA – five phosphonic groups. Radiochemical yield of labeled 99mTc HEDP, OENTMP, EDTMP, PPA is not less than 95%, the radiochemical impurities does not exceed 5%. The investigated compounds have high stability in vivo and selective accumulation in osseous tissue. The highest concentrations of labeled compounds is reached in 3–24 hours after their intravenous injections. The investigated compounds are rapidly excreted from blood and soft organs and tissues mainly through the urinary routes. So present study has showed that these RPP have properties, which making them promising candidates as a diagnostic pharmaceuticals of bone metastases.

  6. Novel sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membrane by an in situ method for direct methanol fuel cells

    Science.gov (United States)

    Wu, Hong; Cao, Ying; Li, Zhen; He, Guangwei; Jiang, Zhongyi

    2015-01-01

    Sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membranes are prepared by an in situ method using titanium tetrachloride (TiCl4) as inorganic precursor and amino trimethylene phosphonic acid (ATMP) as modifier. Phosphonic acid-functionalized titania nanoparticles with a uniform particle size of ∼50 nm are formed and dispersed homogeneously in the SPEEK matrix with good interfacial compatibility. Accordingly, the nanohybrid membranes display remarkably enhanced proton conduction property due to the incorporation of additional sites for proton transport and the formation of well-connected channels by bridging the hydrophilic domains in SPEEK matrix. The nanohybrid membrane with 6 wt. % of phosphonic acid-functionalized titania nanoparticles exhibits the highest proton conductivity of 0.334 S cm-1 at 65 °C and 100% RH, which is 63.7% higher than that of pristine SPEEK membrane. Furthermore, the as-prepared nanohybrid membranes also show elevated thermal and mechanical stabilities as well as decreased methanol permeability.

  7. In vivo inhibition of dipeptidyl peptidase IV activity by pro-pro-diphenyl-phosphonate (Prodipine).

    Science.gov (United States)

    De Meester, I; Belyaev, A; Lambeir, A M; De Meyer, G R; Van Osselaer, N; Haemers, A; Scharpé, S

    1997-07-01

    Dipeptidyl peptidase IV (DPP IV, EC 3.4.14.5), also known as CD26, is a membrane-bound serine protease that cleaves off aminoterminal dipeptides from peptides with a penultimate proline (or, at a much slower rate, a penultimate alanine). Recently, we synthesized and characterized a number of dipeptide-derived diphenylphosphonates. Out of the resulting series of slow-binding irreversible inhibitors of DPP IV, diphenyl 1-(S)-prolylpyrrolidine-2(R,S)-phosphonate hydrochloride (Pro-Pro-diphenylphosphonate or Prodipine) was selected for further study. We investigated the in vivo applicability of Prodipine. Male rabbits weighing 3-4 kg received a single intravenous injection with 10 mg Prodipine or saline. After 1 hr, plasma DPP IV activity had decreased to less than 20% of the preinjection value and remained unchanged during a 24-hr observation period. In a next step, we aimed to study (i) the dose dependency and (ii) the duration of the effect after a single intravenous dose of Prodipine. A profound and long-lasting inhibition of plasma DPP IV activity was observed in the treated animals (1, 5 or 10 mg). It took 5 to 8 days to reach half of the pretreatment DPP IV activity and generally more than 20 days for a complete recovery. Systemic treatment with Prodipine not only led to inhibition of plasma DPP IV activity but also decreased tissue DPP IV activity in circulating mononuclear cells, kidney cortex, thymus, spleen, lung, and liver. No differences in activities of the related peptidases aminopeptidase P (APP, EC 3.4.11.9), prolyl oligopeptidase (PO, EC 3.4.21.26), or aminopeptidase M (mAAP, EC 3.4.11.2) were detected between Prodipine-treated and control rabbits. The in vivo applicability of this chemically stable, irreversible inhibitor of DPP IV opens new possibilities, not only to further unravel the biological functions of this intriguing ectopeptidase, but also to explore this enzyme as a new target in various fields of pharmacological research.

  8. CO2-neutral fuels

    Science.gov (United States)

    Goede, A. P. H.

    2015-08-01

    The need for storage of renewable energy (RE) generated by photovoltaic, concentrated solar and wind arises from the fact that supply and demand are ill-matched both geographically and temporarily. This already causes problems of overcapacity and grid congestion in countries where the fraction of RE exceeds the 20% level. A system approach is needed, which focusses not only on the energy source, but includes conversion, storage, transport, distribution, use and, last but not least, the recycling of waste. Furthermore, there is a need for more flexibility in the energy system, rather than relying on electrification, integration with other energy systems, for example the gas network, would yield a system less vulnerable to failure and better adapted to requirements. For example, long-term large-scale storage of electrical energy is limited by capacity, yet needed to cover weekly to seasonal demand. This limitation can be overcome by coupling the electricity net to the gas system, considering the fact that the Dutch gas network alone has a storage capacity of 552 TWh, sufficient to cover the entire EU energy demand for over a month. This lecture explores energy storage in chemicals bonds. The focus is on chemicals other than hydrogen, taking advantage of the higher volumetric energy density of hydrocarbons, in this case methane, which has an approximate 3.5 times higher volumetric energy density. More importantly, it allows the ready use of existing gas infrastructure for energy storage, transport and distribution. Intermittent wind electricity generated is converted into synthetic methane, the Power to Gas (P2G) scheme, by splitting feedstock CO2 and H2O into synthesis gas, a mixture of CO and H2. Syngas plays a central role in the synthesis of a range of hydrocarbon products, including methane, diesel and dimethyl ether. The splitting is accomplished by innovative means; plasmolysis and high-temperature solid oxygen electrolysis. A CO2-neutral fuel cycle is

  9. CO2-neutral fuels

    Directory of Open Access Journals (Sweden)

    Goede A. P. H.

    2015-01-01

    Full Text Available The need for storage of renewable energy (RE generated by photovoltaic, concentrated solar and wind arises from the fact that supply and demand are ill-matched both geographically and temporarily. This already causes problems of overcapacity and grid congestion in countries where the fraction of RE exceeds the 20% level. A system approach is needed, which focusses not only on the energy source, but includes conversion, storage, transport, distribution, use and, last but not least, the recycling of waste. Furthermore, there is a need for more flexibility in the energy system, rather than relying on electrification, integration with other energy systems, for example the gas network, would yield a system less vulnerable to failure and better adapted to requirements. For example, long-term large-scale storage of electrical energy is limited by capacity, yet needed to cover weekly to seasonal demand. This limitation can be overcome by coupling the electricity net to the gas system, considering the fact that the Dutch gas network alone has a storage capacity of 552 TWh, sufficient to cover the entire EU energy demand for over a month. This lecture explores energy storage in chemicals bonds. The focus is on chemicals other than hydrogen, taking advantage of the higher volumetric energy density of hydrocarbons, in this case methane, which has an approximate 3.5 times higher volumetric energy density. More importantly, it allows the ready use of existing gas infrastructure for energy storage, transport and distribution. Intermittent wind electricity generated is converted into synthetic methane, the Power to Gas (P2G scheme, by splitting feedstock CO2 and H2O into synthesis gas, a mixture of CO and H2. Syngas plays a central role in the synthesis of a range of hydrocarbon products, including methane, diesel and dimethyl ether. The splitting is accomplished by innovative means; plasmolysis and high-temperature solid oxygen electrolysis. A CO2-neutral fuel

  10. LigandRNA: computational predictor of RNA-ligand interactions.

    Science.gov (United States)

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Bujnicki, Janusz M

    2013-12-01

    RNA molecules have recently become attractive as potential drug targets due to the increased awareness of their importance in key biological processes. The increase of the number of experimentally determined RNA 3D structures enabled structure-based searches for small molecules that can specifically bind to defined sites in RNA molecules, thereby blocking or otherwise modulating their function. However, as of yet, computational methods for structure-based docking of small molecule ligands to RNA molecules are not as well established as analogous methods for protein-ligand docking. This motivated us to create LigandRNA, a scoring function for the prediction of RNA-small molecule interactions. Our method employs a grid-based algorithm and a knowledge-based potential derived from ligand-binding sites in the experimentally solved RNA-ligand complexes. As an input, LigandRNA takes an RNA receptor file and a file with ligand poses. As an output, it returns a ranking of the poses according to their score. The predictive power of LigandRNA favorably compares to five other publicly available methods. We found that the combination of LigandRNA and Dock6 into a "meta-predictor" leads to further improvement in the identification of near-native ligand poses. The LigandRNA program is available free of charge as a web server at http://ligandrna.genesilico.pl.

  11. The merits of neutral theory

    NARCIS (Netherlands)

    Alonso, David; Etienne, Rampal S.; McKane, Alan J.

    2006-01-01

    Hubbell's neutral theory of biodiversity has challenged the classic niche-based view of ecological community structure. Although there have been many attempts to falsify Hubbell's theory, we argue that falsification should not lead to rejection, because there is more to the theory than neutrality al

  12. The merits of neutral theory

    NARCIS (Netherlands)

    Alonso, D.; Etienne, R.S.; McKane, A.J.

    2006-01-01

    Hubbell's neutral theory of biodiversity has challenged the classic niche-based view of ecological community structure. Although there have been many attempts to falsify Hubbell's theory, we argue that falsification should not lead to rejection, because there is more to the theory than neutrality al

  13. Neutral evolution of mutational robustness.

    NARCIS (Netherlands)

    Nimwegen, E. van; Crutchfield, J.P.; Huynen, M.A.

    1999-01-01

    We introduce and analyze a general model of a population evolving over a network of selectively neutral genotypes. We show that the population's limit distribution on the neutral network is solely determined by the network topology and given by the principal eigenvector of the network's adjacency ma

  14. Analysis of macromolecules, ligands and macromolecule-ligand complexes

    Science.gov (United States)

    Von Dreele, Robert B [Los Alamos, NM

    2008-12-23

    A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

  15. Ligand-Receptor Interactions

    CERN Document Server

    Bongrand, Pierre

    2008-01-01

    The formation and dissociation of specific noncovalent interactions between a variety of macromolecules play a crucial role in the function of biological systems. During the last few years, three main lines of research led to a dramatic improvement of our understanding of these important phenomena. First, combination of genetic engineering and X ray cristallography made available a simultaneous knowledg of the precise structure and affinity of series or related ligand-receptor systems differing by a few well-defined atoms. Second, improvement of computer power and simulation techniques allowed extended exploration of the interaction of realistic macromolecules. Third, simultaneous development of a variety of techniques based on atomic force microscopy, hydrodynamic flow, biomembrane probes, optical tweezers, magnetic fields or flexible transducers yielded direct experimental information of the behavior of single ligand receptor bonds. At the same time, investigation of well defined cellular models raised the ...

  16. Arene ruthenium(II) complexes with 2-acetamidothiazole derived ligands: Synthesis, structural studies, antifouling and antibacterial properties

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; PrabhaDevi; Sawant, S.G.; Kaminsky, W.

    -acetamidothiazole ligands (L) have been prepared by the reaction of precursor complex [RuCl2(η6-arene)]2 with 2 fold excess of ligand in methanol at room temperature (Scheme 1). All these new complexes 1-4 are neutral and adopted piano stool structure... or NH4PF6also gave the neutral complexes 1-4was unsuccessful even by increasing reaction time and in refluxing condition instead the reactionalso gave the identical neutral complexes1-4. The above results indicated that the reaction of [RuCl2(η6-arene...

  17. Therapeutic androgen receptor ligands

    OpenAIRE

    Allan, George F.; Sui, Zhihua

    2003-01-01

    In the past several years, the concept of tissue-selective nuclear receptor ligands has emerged. This concept has come to fruition with estrogens, with the successful marketing of drugs such as raloxifene. The discovery of raloxifene and other selective estrogen receptor modulators (SERMs) has raised the possibility of generating selective compounds for other pathways, including androgens (that is, selective androgen receptor modulators, or SARMs).

  18. Imidazoline receptors ligands

    Directory of Open Access Journals (Sweden)

    Agbaba Danica

    2012-01-01

    Full Text Available Extensive biochemical and pharmacological studies have determined three different subtypes of imidazoline receptors: I1-imidazoline receptors (I1-IR involved in central inhibition of sympathicus that produce hypotensive effect; I2-imidazoline receptors (I2-IR modulate monoamine oxidase B activity (MAO-B; I3-imidazoline receptors (I3-IR regulate insulin secretion from pancreatic β-cells. Therefore, the I1/I2/I3 imidazoline receptors are selected as new, interesting targets for drug design and discovery. Novel selective I1/I2/I3 agonists and antagonists have been recently developed. In the present review, we provide a brief update to the field of imidazoline research, highlighting some of the chemical diversity and progress made in the 2D-QSAR, 3D-QSAR and quantitative pharmacophore development studies of I1-IR and I2-IR imidazoline receptor ligands. Theoretical studies of I3-IR ligands are not yet performed because of insufficient number of synthesized I3-IR ligands.

  19. Design and optimization of a phosphopeptide anchor for specific immobilization of a capture protein on zirconium phosphonate modified supports.

    Science.gov (United States)

    Liu, Hao; Queffélec, Clémence; Charlier, Cathy; Defontaine, Alain; Fateh, Amina; Tellier, Charles; Talham, Daniel R; Bujoli, Bruno

    2014-11-25

    The attachment of affinity proteins onto zirconium phosphonate coated glass slides was investigated by fusing a short phosphorylated peptide sequence at one extremity to enable selective bonding to the active surface via the formation of zirconium phosphate coordinate covalent bonds. In a model study, the binding of short peptides containing zero to four phosphorylated serine units and a biotin end-group was assessed by surface plasmon resonance-enhanced ellipsometry (SPREE) as well as in a microarray format using fluorescence detection of AlexaFluor 647-labeled streptavidin. Significant binding to the zirconated surface was only observed in the case of the phosphopeptides, with the best performance, as judged by streptavidin capture, observed for peptides with three or four phosphorylation sites and when spotted at pH 3. When fusing similar phosphopeptide tags to the affinity protein, the presence of four phosphate groups in the tag allows efficient immobilization of the proteins and efficient capture of their target.

  20. [Inorganic pyrophosphatase activity of the mouse spleen in the immune response and after treatment with bis-phosphonates].

    Science.gov (United States)

    Komissarenko, S V; Gulaia, N M; Gaĭvoronskaia, G G; Karlova, N P; Tarusova, N B

    1986-01-01

    The inorganic pyrophosphatase activity was determined in different tissues of mice. The immunization of mice by sheep erythrocytes increased the inorganic pyrophosphatase activity of the spleen. The in vivo administration of bisphosphonates (40 mg per 1 g of mass), which are structural analogs of inorganic pyrophosphate (methylene bisphosphonic acid--MBPA, hydroxyethylidene bisphosphonic acid--HEBPA and aminomethylene bisphosphonic acid--AMBPA), inhibited the inorganic pyrophosphatase activity only by MBPA in the thymus and spleen but not in liver. The addition of MBPA, HEBPA as well as of phosphonoacetic acid, imidobisphosphate, bis(phosphonomethyl)-phosphonic acid, MBPA and phosphoric acid monoanhydride to cytosol from the mouse spleen led to the competitive (relative to the [Mg (PPi)2-] complex) inhibition of the inorganic pyrophosphatase activity. AMBPA didn't possess the analogous effect.

  1. Proton conducting graft copolymers with tunable length and density of phosphonated side chains for fuel cell membranes

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja;

    2014-01-01

    matrix. increasing the ionic groups content in the graft copolymers led to extensive membrane swelling. To improve the dimensional stability the graft copolymers were blended with pyridine-modified polysulfone. The blend membranes were transparent with formation of nano-phase domains as revealed from TEM...... gravimetrical analyses. The proton conductivity of membrane prepared from the graft copolymer with the shortest phosphonated side chains was 134 mS cm(-1) at 100 degrees C under fully immersed conditions. The graft copolymer TEM image shows a nanophase separation of ion-rich segments within the polysulfone...... images. The acid-base blend membranes exhibited a slightly higher thermal stability but lower proton conductivity compared to the membranes formed from pure graft copolymers....

  2. Separation of oxidized americium from lanthanides by use of pillared metal(IV) phosphate-phosphonate hybrid materials

    Energy Technology Data Exchange (ETDEWEB)

    Burns, J.D.; Clearfield, A. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry; Borkowski, M.; Reed, D.T. [Los Alamos National Laboratory, Carlsbad, NM (United States). Earth and Environmental Sciences Div.

    2012-07-01

    Closing the nuclear fuel cycle in the US poses many challenges, one of which is found in the waste streams, which contain both trivalent lanthanides and actinides. The separation of americium from the raffinate will dramatically reduce the long-term radiotoxicity of the waste. The sorption of americium in both the tri- and pentavalent oxidation states was observed for four M(IV) phosphate-phosphonate ion exchange materials in nitric acid at pH 2. High selectivity was observed for reduced Am(III) with K{sub d} values ca. 6 x 10{sup 5} mL/g, while the K{sub d} values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO{sub 2}{sup +} to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

  3. Probing the interaction between di- and tri-functionalized carboxy-phosphonic acid and LDH layer structure

    Science.gov (United States)

    Sabbar, El Mouloudi; de Roy, Marie Elisabeth; Leroux, Fabrice

    2006-11-01

    A series of carboxyphosphonate-derivatives of (Zn, Al) layered double hydroxide (LDH) was prepared and characterized by a combination of techniques including powder X-ray diffraction, FTIR spectroscopy and solid-state 13C CP-MAS and 31P MAS NMR spectroscopies. The number of carbon atoms, n=1 or 2 in HO2C(CH2)nPO3H2, was found to have an influence on the accommodation of the interleaved molecule, the carboxylate function lying perpendicular or parallel to the inorganic sheets of the LDH host material. These observations are in agreement with NMR results which evidence an interaction of the interlayered molecules through either the carbonyl or the phosphonate group or both in the case of the larger molecule, N-(phosphonomethyl)iminodiacetic acid. The variation of the basal spacing of the hybrid materials as a function of the temperature indicates a rearrangement of the molecule within the host material gap.

  4. Influence of complexation phenomena with multivalent cations on the analysis of glyphosate and aminomethyl phosphonic acid in water.

    Science.gov (United States)

    Freuze, Ingrid; Jadas-Hecart, Alain; Royer, Alain; Communal, Pierre-Yves

    2007-12-21

    Experimental and theoretical influence of multivalent cations on the analysis of glyphosate and aminomethyl phosphonic acid (AMPA) was studied in pure water and in one surface water. The procedure chosen, based on derivatization with FMOC-Cl, HPLC separation, and fluorescence detection, appears highly affected at cations concentrations current in natural waters. A detailed speciation study performed with the VMINTEQ software strongly suggests that the complexes formed between analytes and cations do not dissociate during the reaction and do not react with the derivatization agent, so that only the free forms are derivatized. These results point out the necessity of a pre-treatment to prevent these interferences, even in low salinity waters. The different ways conceivable are discussed in terms of kinetic and thermodynamic considerations.

  5. The Antiparticles of Neutral Bosons

    CERN Document Server

    Perkins, Walton A

    2013-01-01

    With the advent of the ability to create and study antihydrogen, we think it is appropriate to consider the possibility that antiphotons might not be identical to photons. First of all, we will look at the experimental evidence concerning multiple neutral pions and multiple photons. Because of its internal structure, the neutral kaon is not identical to its antiparticle. We will consider internal structures for the neutral pion and photon for which the antiparticle differs from the particle. Interestingly, the antiphoton thus created from neutrinos does not interact with electrons because its neutrinos have the wrong helicity.

  6. Positional nystagmus showing neutral points.

    Science.gov (United States)

    Hiruma, Kiyoshi; Numata, Tsutomu

    2004-01-01

    We encountered patients who had their static direction-changing positional nystagmus canceled at about 20-30 degrees yaw head rotation from the supine position. This nystagmus was also canceled when the head was rotated 180 degrees from this position. We call these head positions neutral points. At the neutral points, the cupula of the horizontal semicircular canal of the affected ear is positioned vertical to the gravitational plane and no deflection of the cupula occurs. The positional nystagmus observed (except the neutral points) was thought to occur due to a "heavy cupula" or "light cupula", which may be determined by the specific gravity of its endolymph.

  7. Antibody to gp41 MPER alters functional properties of HIV-1 Env without complete neutralization.

    Directory of Open Access Journals (Sweden)

    Arthur S Kim

    2014-07-01

    Full Text Available Human antibody 10E8 targets the conserved membrane proximal external region (MPER of envelope glycoprotein (Env subunit gp41 and neutralizes HIV-1 with exceptional potency. Remarkably, HIV-1 containing mutations that reportedly knockout 10E8 binding to linear MPER peptides are partially neutralized by 10E8, producing a local plateau in the dose response curve. Here, we found that virus partially neutralized by 10E8 becomes significantly less neutralization sensitive to various MPER antibodies and to soluble CD4 while becoming significantly more sensitive to antibodies and fusion inhibitors against the heptad repeats of gp41. Thus, 10E8 modulates sensitivity of Env to ligands both pre- and post-receptor engagement without complete neutralization. Partial neutralization by 10E8 was influenced at least in part by perturbing Env glycosylation. With unliganded Env, 10E8 bound with lower apparent affinity and lower subunit occupancy to MPER mutant compared to wild type trimers. However, 10E8 decreased functional stability of wild type Env while it had an opposite, stabilizing effect on MPER mutant Envs. Clade C isolates with natural MPER polymorphisms also showed partial neutralization by 10E8 with altered sensitivity to various gp41-targeted ligands. Our findings suggest a novel mechanism of virus neutralization by demonstrating how antibody binding to the base of a trimeric spike cross talks with adjacent subunits to modulate Env structure and function. The ability of an antibody to stabilize, destabilize, partially neutralize as well as alter neutralization sensitivity of a virion spike pre- and post-receptor engagement may have implications for immunotherapy and vaccine design.

  8. Preparation, characterization and application of N-methylene phosphonic acid chitosan grafted magnesia–zirconia stationary phase

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qing; Chen, Jie; Huang, Kun; Zhang, Xin; Xu, Li [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Shi, Zhi-guo, E-mail: shizg@whu.edu.cn [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2015-01-07

    Highlights: • N-methylene phosphonic acid chitosan grafted MgO–ZrO{sub 2} was prepared. • It exhibited superior HILIC chromatographic performance to the bare MgO–ZrO{sub 2}. • Monosaccharides, phospholipids and peptides were successfully separated. • It was a promising HILIC stationary phase. - Abstract: A hydrophilic stationary phase (SP) was prepared through grafting N-methylene phosphonic acid chitosan on magnesia–zirconia particles (P-CTS-MgO–ZrO{sub 2}) via Lewis acid–base interaction. The resulting material was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscope and nitrogen adsorption analysis. The chromatographic performance of P-CTS-MgO–ZrO{sub 2} was systemically evaluated by studying effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the novel SP provided hydrophilic, electrostatic-repulsion and ion-exchange interactions. Compared to the bare MgO–ZrO{sub 2}, P-CTS-MgO–ZrO{sub 2} exhibited superior peak shape, reasonable resolution and reduced analysis time in separation of basic analytes. Besides, remarkable resolving power of acids, i.e. six non-steroidal anti-inflammatory drugs which failed to be eluted from the bare MgO–ZrO{sub 2}, was obtained with the theoretical plate number (N/m) of 4653–31313, asymmetry factor <1.21 and the resolution of 1.6–3.4. Finally, P-CTS-MgO–ZrO{sub 2} SP was applied to separate monosaccharides, phospholipids and peptides. P-CTS-MgO–ZrO{sub 2} was a promising hydrophilic SP for wide applications.

  9. Bexarotene ligand pharmaceuticals.

    Science.gov (United States)

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  10. Neutrality Versus Materiality: A Thermodynamic Theory of Neutral Surfaces

    Directory of Open Access Journals (Sweden)

    Rémi Tailleux

    2016-09-01

    Full Text Available In this paper, a theory for constructing quasi-neutral density variables γ directly in thermodynamic space is formulated, which is based on minimising the absolute value of a purely thermodynamic quantity J n . Physically, J n has a dual dynamic/thermodynamic interpretation as the quantity controlling the energy cost of adiabatic and isohaline parcel exchanges on material surfaces, as well as the dependence of in-situ density on spiciness, in a description of water masses based on γ, spiciness and pressure. Mathematically, minimising | J n | in thermodynamic space is showed to be equivalent to maximising neutrality in physical space. The physics of epineutral dispersion is also reviewed and discussed. It is argued, in particular, that epineutral dispersion is best understood as the aggregate effect of many individual non-neutral stirring events (being understood here as adiabatic and isohaline events with non-zero buoyancy, so that it is only the net displacement aggregated over many events that is approximately neutral. This new view resolves an apparent paradox between the focus in neutral density theory on zero-buoyancy motions and the overwhelming evidence that lateral dispersion in the ocean is primarily caused by non-zero buoyancy processes such as tides, residual currents and sheared internal waves. The efficiency by which a physical process contributes to lateral dispersion can be characterised by its energy signature, with those processes releasing available potential energy (negative energy cost being more efficient than purely neutral processes with zero energy cost. The latter mechanism occurs in the wedge of instability, and its source of energy is the coupling between baroclinicity, thermobaricity, and density compensated temperature/salinity anomalies. Such a mechanism, which can only exist in a salty ocean, is speculated to be important for dissipating spiciness anomalies and neutral helicity. The paper also discusses potential

  11. Incomplete Neutralization and Deviation from Sigmoidal Neutralization Curves for HIV Broadly Neutralizing Monoclonal Antibodies.

    Directory of Open Access Journals (Sweden)

    Laura E McCoy

    2015-08-01

    Full Text Available The broadly neutralizing HIV monoclonal antibodies (bnMAbs PG9, PG16, PGT151, and PGT152 have been shown earlier to occasionally display an unusual virus neutralization profile with a non-sigmoidal slope and a plateau at <100% neutralization. In the current study, we were interested in determining the extent of non-sigmoidal slopes and plateaus at <100% for HIV bnMAbs more generally. Using both a 278 panel of pseudoviruses in a CD4 T-cell (U87.CCR5.CXCR4 assay and a panel of 117 viruses in the TZM-bl assay, we found that bnMAbs targeting many neutralizing epitopes of the spike had neutralization profiles for at least one virus that plateaued at <90%. Across both panels the bnMAbs targeting the V2 apex of Env and gp41 were most likely to show neutralization curves that plateaued <100%. Conversely, bnMAbs targeting the high-mannose patch epitopes were less likely to show such behavior. Two CD4 binding site (CD4bs Abs also showed this behavior relatively infrequently. The phenomenon of incomplete neutralization was also observed in a large peripheral blood mononuclear cells (PBMC-grown molecular virus clone panel derived from patient viral swarms. In addition, five bnMAbs were compared against an 18-virus panel of molecular clones produced in 293T cells and PBMCs and assayed in TZM-bl cells. Examples of plateaus <90% were seen with both types of virus production with no consistent patterns observed. In conclusion, incomplete neutralization and non-sigmoidal neutralization curves are possible for all HIV bnMAbs against a wide range of viruses produced and assayed in both cell lines and primary cells with implications for the use of antibodies in therapy and as tools for vaccine design.

  12. Zr (IV COMPLEXES OF SOME NITROGEN-OXYGEN DONOR LIGANDS (SEMICARBAZONES & SALICYLALDAZINE

    Directory of Open Access Journals (Sweden)

    Z F DAWOOD

    2002-06-01

    Full Text Available Complexes containing mixed ligands of zirconium (IV have been synthesized by the reaction of zirconium (IV nitrate (Zr(NO34, 5H2O with salicylaldazine (SAH2 and semicarbazone ligands benzaldehyde semicarbazone (BSCH, 4-methoxybenzaldehyde semicarbzone (MBSCH, 2-chlorobenzaldehyde semicrbazone (CISCH and cinnamaldehyde semicarbazone (CinSCH forming complexes of the type [Zr2(SAH2(SCH2](NO38 and [Zr2(SA2 (SC2](NO32 in neutral and basic medium respectively. The ligands and their complexes are characterized physico-chemically.

  13. Neutral theory in community ecology

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    One of the central goals of community ecology is to understand the forces that maintain species diversity within communities. The traditional niche-assembly theory asserts that species live together in a community only when they differ from one another in resource uses. But this theory has some difficulties in explaining the diversity often observed in specie-rich communities such as tropical forests. As an alternative to the niche theory, Hubbell and other ecologists introduced a neutral model. Hubbell argues that the number of species in a community is controlled by species extinction and immigration or speciation of new species. Assuming that all individuals of all species in a trophically similar com-munity are ecologically equivalent, Hubbell's neutral theory predicts two important statistical distributions. One is the asymptotic log-series distribution for the metacommunities under point mutation speciation, and the other is the zero-sum multinomial distribution for both local communities under dispersal limitation and metacommunities under random fission speciation. Unlike the niche-assembly theory, the neutral theory takes similarity in species and individuals as a starting point for investigating species diversity. Based on the fundamental processes of birth, death, dispersal and spe-ciation, the neutral theory provided the first mechanistic explanation of species abundance distribution commonly observed in natural communities. Since the publication of the neutral theory, there has been much discussion about it, pro and con. In this paper, we summarize recent progress in the assumption, prediction and speciation mode of the neutral theory, including progress in the theory itself, tests about the assumption of the theory, prediction and speciation mode at the metacommunity level. We also suggest that the most important task in the future is to bridge the niche-assembly theory and the neutral theory, and to add species differences to the neutral theory and

  14. Vendor neutral archive in PACS

    Directory of Open Access Journals (Sweden)

    Tapesh Kumar Agarwal

    2012-01-01

    Full Text Available An archive is a location containing a collection of records, documents, or other materials of historical importance. An integral part of Picture Archiving and Communication System (PACS is archiving. When a hospital needs to migrate a PACS vendor, the complete earlier data need to be migrated in the format of the newly procured PACS. It is both time and money consuming. To address this issue, the new concept of vendor neutral archive (VNA has emerged. A VNA simply decouples the PACS and workstations at the archival layer. This is achieved by developing an application engine that receives, integrates, and transmits the data using the different syntax of a Digital Imaging and Communication in Medicine (DICOM format. Transferring the data belonging to the old PACS to a new one is performed by a process called migration of data. In VNA, a number of different data migration techniques are available to facilitate transfer from the old PACS to the new one, the choice depending on the speed of migration and the importance of data. The techniques include simple DICOM migration, prefetch-based DICOM migration, medium migration, and the expensive non-DICOM migration. "Vendor neutral" may not be a suitable term, and "architecture neutral," "PACS neutral," "content neutral," or "third-party neutral" are probably better and preferred terms. Notwithstanding this, the VNA acronym has come to stay in both the medical IT user terminology and in vendor nomenclature, and radiologists need to be aware of its impact in PACS across the globe.

  15. Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces.

    Science.gov (United States)

    Hyde, Jacob T; Hanson, Kenneth; Vannucci, Aaron K; Lapides, Alexander M; Alibabaei, Leila; Norris, Michael R; Meyer, Thomas J; Harrison, Daniel P

    2015-05-13

    The oxidative stability of the molecular components of dye-sensitized photoelectrosynthesis cells for solar water splitting remains to be explored systematically. We report here the results of an electrochemical study on the oxidative stability of ruthenium(II) polypyridyl complexes surface-bound to fluorine-doped tin oxide electrodes in acidic solutions and, to a lesser extent, as a function of pH and solvent with electrochemical monitoring. Desorption occurs for the Ru(II) forms of the surface-bound complexes with oxidation to Ru(III) enhancing both desorption and decomposition. Based on the results of long-term potential hold experiments with cyclic voltammetry monitoring, electrochemical oxidation to Ru(III) results in slow decomposition of the complex by 2,2'-bipyridine ligand loss and aquation and/or anation. A similar pattern of ligand loss was also observed for a known chromophore-catalyst assembly for both electrochemical water oxidation and photoelectrochemical water splitting. Our results are significant in identifying the importance of enhancing chromophore stability, or at least transient stability, in oxidized forms in order to achieve stable performance in aqueous environments in photoelectrochemical devices.

  16. (E)- and (Z)-stereodefined enol phosphonates derived from β-ketoesters: stereocomplementary synthesis of fully-substituted α,β-unsaturated esters.

    Science.gov (United States)

    Nakatsuji, Hidefumi; Ashida, Yuichiro; Hori, Hiroshi; Sato, Yuka; Honda, Atsushi; Taira, Mayu; Tanabe, Yoo

    2015-08-14

    A versatile, robust, and stereocomplementary synthesis of fully-substituted (E)- and (Z)-stereodefined α,β-unsaturated esters 3 from accessible α-substituted β-ketoesters 1via (E)- and (Z)-enol phosphonates was achieved. The present method involves two accessible reaction sequences: (i) (E)- and (Z)-stereocomplementary enol phosphorylations of a wide variety of β-ketoesters 1 (24 examples; 71–99% yield, each >95: 5 ds), and (ii) (E)- and (Z)-stereoretentive Suzuki–Miyaura cross-coupling (16 examples; 71–91% yield, >81/19 ds) and Negishi cross-coupling (32 examples; 65–96% yield, >95 : 5 ds) using (E)- and (Z)-enol phosphonates 2. 1H-NMR monitoring for a key reactive N-phosphorylammonium (imidazolium) intermediate I and an application in the synthesis of both (E)- and (Z)-tamoxifen precursors 6 are described.

  17. A Rapid One-Pot Synthesis of Novel High-Purity Methacrylic Phosphonic Acid (PA-Based Polyhedral Oligomeric Silsesquioxane (POSS Frameworks via Thiol-Ene Click Reaction

    Directory of Open Access Journals (Sweden)

    K. Karuppasamy

    2017-05-01

    Full Text Available Herein, we demonstrate a facile methodology to synthesis a novel methacrylic phosphonic acid (PA-functionalized polyhedral oligomeric silsesquioxanes (POSSs via thiol-ene click reaction using octamercapto thiol-POSS and ethylene glycol methacrylate phosphate (EGMP monomer. The presence of phosphonic acid moieties and POSS-cage structure in POSS-S-PA was confirmed by Fourier transform infrared (FT-IR and nuclear magnetic resonance (1H, 29Si and 31P-NMR analyses. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF mass spectrum of POSS-S-PA acquired in a dithranol matrix, which has specifically designed for intractable polymeric materials. The observed characterization results signposted that novel organo-inorganic hybrid POSS-S-PA would be an efficacious material for fuel cells as a proton exchange membrane and high-temperature applications due to its thermal stability of 380 °C.

  18. Radiochemical studies of {sup 99m}Tc complexes of modified cysteine ligands and bifunctional chelating agents

    Energy Technology Data Exchange (ETDEWEB)

    Pillai, M.R.A. E-mail: ambi@magnum.barc.ernet.in; Kothari, Kanchan; Banerjee, Sharmila; Samuel, Grace; Suresh, Manju; Sarma, H.D.; Jurisson, S

    1999-07-01

    The synthesis of four novel ligands using the amino-acid cysteine and its ethyl carboxylate derivative is described. The synthetic method involves a two-step procedure, wherein the intermediate Schiff base formed by the condensation of the amino group of the cysteine substrate and salicylaldehyde is reduced to give the target ligands. The intermediates and the final products were characterized by high resolution nuclear magnetic resonance spectroscopy. Complexation studies of the ligands with {sup 99m}Tc were optimized using stannous tartrate as the reducing agent under varying reaction conditions. The complexes were characterized using standard quality control techniques such as thin layer chromatography, paper electrophoresis, and paper chromatography. Lipophilicities of the complexes were estimated by solvent extraction into chloroform. Substantial changes in net charge and lipophilicity of the {sup 99m}Tc complexes were observed on substituting the carboxylic acid functionality in ligands I and II with the ethyl carboxylate groups (ligands III and IV). All the ligands formed {sup 99m}Tc complexes in high yield. Whereas the complexes with ligands I and II were observed to be hydrophilic in nature and not extractable into CHCl{sub 3}, ligands III and IV resulted in neutral and lipophilic {sup 99m}Tc complexes. The {sup 99m}Tc complex with ligand III was not stable and on storage formed a hydrophilic and nonextractable species. The biodistribution of the complexes of ligands I and II showed that they cleared predominantly through the kidneys, whereas the complexes with ligands III and IV were excreted primarily through the hepatobiliary system. No significant brain uptake was observed with the {sup 99m}Tc complexes with ligands III and IV despite their favorable properties of neutrality, lipophilicity, and conversion into a hydrophilic species. These ligands offer potential for use as bifunctional chelating agents.

  19. p-Phosphonic acid calix[8]arene assisted dispersion and stabilisation of pea-pod C60@multi-walled carbon nanotubes in water.

    Science.gov (United States)

    Chen, Xianjue; Gibson, Christopher T; Britton, Joshua; Eggers, Paul K; Wahid, M Haniff; Raston, Colin L

    2015-02-11

    A facile approach has been developed for non-covalently stabilising pristine C60 and multi-walled carbon nanotubes (MWCNTs) in water in the presence of p-phosphonic acid calix[8]arene, along with the formation of a 'pea-pod' encapsulation of the fullerene inside the MWCNTs. Aqueous dispersions of the different carbon nano-materials are readily decorated with palladium nanoparticles.

  20. Melatonin: functions and ligands.

    Science.gov (United States)

    Singh, Mahaveer; Jadhav, Hemant R

    2014-09-01

    Melatonin is a chronobiotic substance that acts as synchronizer by stabilizing bodily rhythms. Its synthesis occurs in various locations throughout the body, including the pineal gland, skin, lymphocytes and gastrointestinal tract (GIT). Its synthesis and secretion is controlled by light and dark conditions, whereby light decreases and darkness increases its production. Thus, melatonin is also known as the 'hormone of darkness'. Melatonin and analogs that bind to the melatonin receptors are important because of their role in the management of depression, insomnia, epilepsy, Alzheimer's disease (AD), diabetes, obesity, alopecia, migraine, cancer, and immune and cardiac disorders. In this review, we discuss the mechanism of action of melatonin in these disorders, which could aid in the design of novel melatonin receptor ligands.

  1. Design of new phosphonic acid monomers for dental adhesives--synthesis of (meth) acryloxyalkyl 3-phosphonopropionates and evaluation of their adhesion-promoting functions.

    Science.gov (United States)

    Ikemura, Kunio; Tay, Franklin R; Nishiyama, Nonrihiro; Pashley, David H; Endo, Takeshi

    2006-09-01

    The aims of this study were to synthesize new phosphonic acid monomers, and to examine their bonding performance. Four kinds of newly designed phosphonic acid monomers were synthesized, and seven experimental composite-type adhesive resins comprising the synthesized monomers (3 wt%), with BPO/DEPT/BPBA initiator were prepared. Tensile bond strengths of the adhesive resins to enamel and metal were measured with a universal testing machine at a crosshead speed of 1.0 mm/ min. The synthesized adhesive monomers were light yellow viscous liquids with 32.5%-49.3% yields, and identified by 1H NMR, IR and elemental analysis to be (meth)acryloxyalkyl 3-phosphonopropionates [R-P(=O) (OH)2] (5-MPPP, 6-MHPP, 6-AHPP, 10-MDPP). It was found that the newly developed phosphonic acid monomers with BPO/DEPT/BPBA initiator attained strong adhesion to both unetched, ground enamel and sandblasted Ni-Cr alloy with good durability. They exhibited significantly higher bond strengths than conventional phosphorous-containing monomers such as MEPP and VBPA (p adhesive resins have potential prosthodontic and orthodontic applications, especially as self-etching, non-rinsing orthodontic adhesive resins.

  2. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

    Science.gov (United States)

    Dietrich, Bernard

    1985-01-01

    Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

  3. Ligand-guided pathway selection in nickel-catalyzed couplings of enals and alkynes.

    Science.gov (United States)

    Li, Wei; Montgomery, John

    2012-01-28

    Nickel-catalyzed couplings of enals and alkynes utilizing triethylborane as the reducing agent illustrate a significant dependence on ligand structure. Simple variation of monodentate phosphines allows selective access to alkylative couplings or reductive cycloadditions, while further variation of reaction conditions provides clean access to reductive couplings and redox-neutral couplings.

  4. CuI complexes with a noninnocent PNP Ligand: selective dearomatization and electrophilic addition reactivity

    NARCIS (Netherlands)

    van der Vlugt, J.I.; Pidko, E.A.; Vogt, D.; Lutz, M.; Spek, A.L.

    2009-01-01

    The neutral, T-shaped complex CuI(PN−PtBu) (2), featuring a dearomatized 2,6-bis(diphosphino)pyridine (PNP)-pincer ligand, is shown to interact rapidly with electrophiles. This has enabled the synthesis of acetato complex 3. Furthermore, C−C bond formation onto the deprotonated methylene-bridgehead

  5. Cu-I complexes with a noninnocent PNP ligand: Selective dearomatization and electrophilic addition reactivity

    NARCIS (Netherlands)

    van der Vlugt, J.I.; Pidko, E.A.; Vogt, D.; Lutz, M.; Spek, A.L.

    2009-01-01

    The neutral, T-shaped complex Cu-I((PN-PtBu)) (2), featuring a dearomatized 2,6-bis(diphosphino)pyridine (PNP)-pincer ligand, is shown to interact rapidly with electrophiles. This has enabled the synthesis of acetato complex 3. Furthermore, C-C bond formation onto the deprotonated methylene-bridgehe

  6. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    G-quadruplex stabilizing compounds have recently received increased interest due to their potential application as anticancer therapeutics. A significant number of structurally diverse G-quadruplex ligands have been developed. Some of the most potent and selective ligands currently known are macr...

  7. A computational study of ligand binding affinities in iron(III) porphine and protoporphyrin IX complexes.

    Science.gov (United States)

    Durrant, Marcus C

    2014-07-01

    The search for novel anti-malarial drugs that can disrupt biomineralization of ferriprotoporphyrin IX to haemozoin requires an understanding of the fundamental chemistry of the porphyrin's iron(iii) centre at the water-lipid interface. Towards this end, the binding affinities for a diverse set of 31 small ligands with iron(iii) porphine have been calculated using density functional theory, in the gas phase and also with implicit solvent corrections for both water and n-octanol. In addition, the binding of hydroxide, chloride, acetate, methylamine and water to ferriprotoporphyrin IX has been studied, and very similar trends are observed for the smaller and larger models. Anionic ligands generally give stronger binding than neutral ones; the strongest binding is observed for RO(-) and OH(-) ligands, whilst acetate binds relatively weakly among the anions studied. Electron-rich nitrogen donors tend to bind more strongly than electron-deficient ones, and the weakest binding is found for neutral O and S donors such as oxazole and thiophene. In all cases, ligand binding is stronger in n-octanol than in water, and the differences in binding energies for the two solvents are greater for ionic ligands than for neutrals. Finally, dimerization of ferriprotoporphyrin IX by means of iron(iii)-carboxylate bond formation has been modelled. The results are discussed in terms of haemozoin crystal growth and its disruption by known anti-malarial drugs.

  8. Neutral hydrogen in galactic fountains

    CERN Document Server

    Booth, C M

    2007-01-01

    Simulations of an isolated Milky Way-like galaxy, in which supernovae power a galactic fountain, reproduce the observed velocity and 21cm brightness statistics of galactic neutral hydrogen (HI). The simulated galaxy consists of a thin HI disk, similar in extent and brightness to that observed in the Milky Way, and extra-planar neutral gas at a range of velocities due to the galactic fountain. Mock observations of the neutral gas resemble the HI flux measurements from the Leiden-Argentine-Bonn (LAB) HI, survey, including a high-velocity tail which matches well with observations of high-velocity clouds. The simulated high-velocity clouds are typically found close to the galactic disk, with a typical line-of-sight distance of 13kpc from observers on the solar circle. The fountain efficiently cycles matter from the centre of the galaxy to its outskirts at a rate of around 0.5 M_sun/yr

  9. Neutral B meson flavor tagging

    Science.gov (United States)

    Wilson, Robert J.

    2001-07-01

    We present an investigation of the use of net charge and kaon identification to tag the flavor of neutral B mesons. The net charge of the neutral B meson decay products is zero if all charged particles are used and slightly non-zero if only undiscriminated hadronic final states are used. The net charge of the kaons alone correctly tags the identity of the neutral meson in at least a third of all decays. We have parametrized the particle identification capability of several techniques, such as dE/dx in time projection chambers, LEP/SLC ring-imaging chambers and an enhanced BaBar DIRC. Using these parametrisations we compare the relative tagging power of each technique to that of an ideal detector.

  10. Neutral B meson flavor tagging

    CERN Document Server

    Wilson, R J

    2001-01-01

    We present an investigation of the use of net charge and kaon identification to tag the flavor of neutral B mesons. The net charge of the neutral B meson decay products is zero if all charged particles are used and slightly non-zero if only undiscriminated hadronic final states are used. The net charge of the kaons alone correctly tags the identity of the neutral meson in at least a third of all decays. We have parametrized the particle identification capability of several techniques, such as dE/dx in time projection chambers, LEP/SLC ring-imaging chambers and an enhanced BaBar DIRC. Using these parametrisations we compare the relative tagging power of each technique to that of an ideal detector. (8 refs).

  11. Structural basis of selectivity and neutralizing activity of a TGFα/epiregulin specific antibody.

    Science.gov (United States)

    Boyles, Jeffrey S; Atwell, Shane; Druzina, Zhanna; Heuer, Josef G; Witcher, Derrick R

    2016-11-01

    Recent studies have implicated a role of the epidermal growth factor receptor (EGFR) pathway in kidney disease. Skin toxicity associated with therapeutics which completely block the EGFR pathway precludes their use in chronic dosing. Therefore, we developed antibodies which specifically neutralize the EGFR ligands TGFα (transforming growth factor-alpha) and epiregulin but not EGF (epidermal growth factor), amphiregulin, betacellulin, HB-EGF (heparin-binding epidermal growth factor), or epigen. The epitope of one such neutralizing antibody, LY3016859, was characterized in detail to elucidate the structural basis for ligand specificity. Here we report a crystal structure of the LY3016859 Fab fragment in complex with soluble human TGFα. Our data demonstrate a conformational epitope located primarily within the C-terminal subdomain of the ligand. In addition, point mutagenesis experiments were used to highlight specific amino acids which are critical for both antigen binding and neutralization, most notably Ala(41) , Glu(44) , and His(45) . These results illustrate the structural basis for the ligand specificity/selectivity of LY3016859 and could also provide insight into further engineering to alter specificity and/or affinity of LY3016859. © 2016 The Protein Society.

  12. Surface-enhanced Raman scattering studies on the interaction of phosphonate derivatives of imidazole, thiazole, and pyridine with a silver electrode in aqueous solution.

    Science.gov (United States)

    Podstawka, Edyta; Kudelski, Andrzej; Olszewski, Tomasz K; Boduszek, Bogdan

    2009-07-23

    Surface-enhanced Raman scattering (SERS) spectra from phosphonate derivatives of N-heterocyclic aromatic compounds immobilized on an electrochemically roughened silver electrode surface are reported and compared to Raman spectra of the corresponding solid species. The tested compounds contain imidazole [ImMeP ([hydroxy-(1H-imidazol-5-yl)-methyl]-phosphonic acid) and (ImMe)2P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]-phosphinic acid)]; thiazole [BAThMeP ((butylamino-thiazol-2-yl-methyl)-phosphonic acid) and BzAThMeP ((benzylamino-thiazol-2-yl-methyl)-phosphonic acid)]; and pyridine ((PyMe)2P (bis[(hydroxy-pyridin-3-yl-methyl)]-phosphinic acid) aromatic rings. Changes in wavenumber, broadness, and the enhancement of N-heterocyclic aromatic ring bands upon adsorption are consistent with the adsorption primarily occurring through the N lone pair of electrons with the ring arranged in a largely edge-on manner for ImMeP and BzAThMeP or in a slightly inclined orientation to the silver electrode surface at an intermediate angle from the surface normal for (ImMe)2P, BAThMeP, and (PyMe)2P. A strong enhancement of a roughly 1500 cm(-1) SERS signal for ImMeP and (PyMe)2P is also observed. This phenomenon is attributed to the formation of a localized C=C bond, which is accompanied by a decrease in the ring-surface pi-electrons' overlap. In addition, more intense SERS bands due to the benzene ring in BzAThMeP are observed than those observed for the thiazole ring, which suggests a preferential adsorption of benzene. Some interaction of a phosphonate unit is also suggested but with moderate strength between biomolecules. The strength of the P=O coordination to the silver electrode is highest for ImMeP but lowest for BzAThMeP. For all studied biomolecules, the contribution of the structural components to their ability to interact with their receptors was correlated with the SERS patterns.

  13. Traps for neutral radioactive atoms

    CERN Document Server

    Sprouse, G D; Grossman, J S; Orozco, L A; Pearson, M R

    2002-01-01

    We describe several methods for efficiently injecting a small number of radioactive atoms into a laser trap. The characteristics of laser traps that make them desirable for physics experiments are discussed and several different experimental directions are described. We describe recent experiments with the alkali element Fr and point to future directions of the neutral atom trapping program.

  14. Neutral Models with Generalised Speciation

    NARCIS (Netherlands)

    Haegeman, Bart; Etienne, Rampal S.

    Hubbell's neutral theory claims that ecological patterns such as species abundance distributions can be explained by a stochastic model based on simple assumptions. One of these assumptions, the point mutation assumption, states that every individual has the same probability to speciate. Etienne et

  15. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea;

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA......-ray crystallographic analyses, chemical correlation, and CD spectral analyses. The effects of the individual stereoisomers at ionotropic and metabotropic (S)-Glu receptors (iGluRs and mGluRs) were characterized. Compounds with S-configuration at the alpha-carbon generally showed mGluR2 agonist activity of similar...... limited effect on pharmacology. Structure-activity relationships at iGluRs in the rat cortical wedge preparation showed a complex pattern, some compounds being NMDA receptor agonists [e.g., EC(50) =110 microM for (2S,5RS)-5-methyl-AA (6a,b)] and some compounds showing NMDA receptor antagonist effects [e...

  16. Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Abou-Dobara, M. I.; Seyam, H. A.

    2013-03-01

    A novel series of copper(II) and palladium(II) with 4-derivatives benzaldehyde pyrazolone (Ln) were synthesized. The mixed ligand complexes were prepared by using 1,10-phenanthroline (Phen) as second ligand. The structure of these complexes was identified and confirm by elemental analysis, molar conductivity, UV-Vis, IR and 1H NMR spectroscopy and magnetic moment measurements as well as thermal analysis. The ligand behaves as a neutral bidentate ligand through ON donor sites. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(Ln)2]Cl2ṡ2H2O. Schiff bases (Ln) were tested against bacterial species; namely two Gram positive bacteria (Staphylococcus aureus and Bacillus cereus) and two Gram negative bacteria (Escherichia coli and Klebsiella pneumoniae) and fungal species (Aspergillus niger, Fusarium oxysporium, Penicillium italicum and Alternaria alternata). The tested compounds have antibacterial activity against S. aureus, B. cereus and K. pneumoniae.

  17. Synthesis and Biological Activity Evaluation of Novel α-Amino Phosphonate Derivatives Containing a Pyrimidinyl Moiety as Potential Herbicidal Agents.

    Science.gov (United States)

    Chen, Jin-Long; Tang, Wu; Che, Jian-Yi; Chen, Kai; Yan, Gang; Gu, Yu-Cheng; Shi, De-Qing

    2015-08-19

    To find novel high-activity and low-toxicity herbicide lead compounds with novel herbicidal mode of action, series of novel α-amino phosphonate derivatives containing a pyrimidinyl moiety, I, II, III, and IV, were designed and synthesized by Lewis acid (magnesium perchlorate) catalyzed Mannich-type reaction of aldehydes, amines, and phosphites. Their structures were clearly identified by spectroscopy data (IR, (1)H NMR, (31)P NMR, EI-MS) and elemental analyses. The bioassay [in vitro, in vivo (GH1 and GH2)] showed that most compounds I exhibited good herbicidal activities; for example, the activities of compounds Ib, Ic, Ig, Ii, Ik, and Im were as good as the positive control herbicides (acetochlor, atrazine, mesotrione, and glyphosate). However, their structural isomers II and III and analogues IV did not display any herbicidal activities in vivo, although some of them possessed selective inhibitory activity against Arabidopsis thaliana in vitro. Interestingly, it was found that compounds IVs, IVt, and IVl showed selective insecticidal activities against Aphis species or Plutella xylostella, respectively. Their preliminary herbicidal mode of action and structure-activity relationships were also studied.

  18. Synthesis and Crystal Structure of Diethyl (4,6-diamino-1,3,5-triazine-2-yl) phosphonate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The crystal of the title compound diethyl (4,6-diamino-1,3,5-triazine-2-yl) phosphonate, (C14H28N10O6P2, Mr=494.40), has been prepared and determined by X-ray single crystal diffraction. The crystal belongs to the triclinic system, space group P with parameters: a=8.398(1) , b=10.206(1), c=14.538(2), α=75.221(3), β=85.965(3), γ=81.746(3)°, V=1191.6(3)3, S=1.028, Z=2, Dc=1.378Mg/m3, μ=0.233mm-1, F(000)=520, λ(MoKα)=0.71073, T=293(2)K, final R=0.071 and wR=0.1953 for 4177 independent reflections with I≥2σ(I). In the title compound, each molecule is linked to five neighbour molecules by hydrogen bonds forming layers perpendicular to the a axis and molecules in each layer are linked by a two-dimensional network of hydrogen bonds in the bc plane.

  19. Preparation of a Novel Calcium Phosphate Cement Using N-methylene Phosphonic Chitosan as a Gelling Agent

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A modified chitosan ( N-methylene phosphonic Chitosan, NMPC ) was synthesized to improve solubility and ability to bind calcium ion. The properties of the raw material chitosan and its derivative NMPC were characterized using FTIR, 1 H-NMR. The aim of this study was to enhance the compressive CPC by reinforcing with NMPC. A formulation consisting of CPC powder, buffer solution and gelling agent was used for preparation of the CPC. CPC powder consisted of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous ( DCPA ). NMPC which acted as the gelling agent was dissolved iuto KH2 PO4 -Na2 HPO4 buffer solution. Each specimen in the mold was sandwiched between two fritted glass sides and kept for 24 hours. Compressive strengths were determined, the setting product was identified using X-ray diffraction and scanning electron microscopy was used to investigate the hydroxyapatite particles size and porosity. The experimental results showed that the dominating influence on the compressive strengths of CPC-NMPC was the HA particle size, its uniformity and appropriate porosity.

  20. Energy-Level Engineering at ZnO/Oligophenylene Interfaces with Phosphonate-Based Self-Assembled Monolayers.

    Science.gov (United States)

    Timpel, Melanie; Nardi, Marco V; Ligorio, Giovanni; Wegner, Berthold; Pätzel, Michael; Kobin, Björn; Hecht, Stefan; Koch, Norbert

    2015-06-10

    We used aromatic phosphonates with substituted phenyl rings with different molecular dipole moments to form self-assembled monolayers (SAMs) on the Zn-terminated ZnO(0001) surface in order to engineer the energy-level alignment at hybrid inorganic/organic semiconductor interfaces, with an oligophenylene as organic component. The work function of ZnO was tuned over a wide range of more than 1.7 eV by different SAMs. The difference in the morphology and polarity of the SAM-modified ZnO surfaces led to different oligophenylene orientation, which resulted in an orientation-dependent ionization energy that varied by 0.7 eV. The interplay of SAM-induced work function modification and oligophenylene orientation changes allowed tuning of the offsets between the molecular frontier energy levels and the semiconductor band edges over a wide range. Our results demonstrate the versatile use of appropriate SAMs to tune the energy levels of ZnO-based hybrid semiconductor heterojunctions, which is important to optimize its function, e.g., targeting either interfacial energy- or charge-transfer.

  1. Synthesis and Crystal Structure of Diethyl 5-Acetoxy-3-(4-chlorophenyl)-4,5-dihydroisoxazol-5-yl-5-phosphonate

    Institute of Scientific and Technical Information of China (English)

    SHANG Zhi-Qiang; CHEN Ru-Yu; HUANG You

    2006-01-01

    The crystal structure of the title compound, diethyl 5-acetoxy-3-(4-chlorophenyl)-4,5-dihydroisoxazol-5-yl-5-phosphonate (Ci5H19ClNO6P, Mr = 375.73), has been synthesized by the treatment of nitrile oxides and 1-acetyloxy-vinylphosphonate under very mild conditions in good yields, and determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group C2/c with a = 16.914(10), b = 10.567(7), c = 21.927(13)(A),β = 110.249(11)°, V= 3677(4)(A)3,Z = 8, Dc = 1.358 g/cm3, F(000) = 1568, μ(MoKa) = 0.324 mm-1, S = 1.011, the final R = 0.0661and wR = 0.1556. The X-ray analytic results showed that the dihedral angle between the phenyl group and the isoxazoline ring is 10.7°.

  2. Bioavailability and bioconcentration potential of perfluoroalkyl-phosphinic and -phosphonic acids in zebrafish (Danio rerio): Comparison to perfluorocarboxylates and perfluorosulfonates.

    Science.gov (United States)

    Chen, Fangfang; Gong, Zhiyuan; Kelly, Barry C

    2016-10-15

    Currently, information regarding bioavailability and bioconcentration potential of perfluoroalkyl phosphinic acids (PFPiAs) in aquatic organisms does not exist. The main objective of the present study was to assess uptake and elimination kinetics of PFPiAs in zebrafish (Danio rerio) following aqueous exposure. The results showed that PFPiA exposure can result in very high steady-state bioconentration factors (BCFss), compared to perfluorocarboxylates and perfluorosulfonates.C6/C10 PFPiA exhibited the highest BCFss, ranging between 10(7) and 10(10), orders of magnitude higher than those for long-chain perfluorocarboxylates. Strong positive relationships were observed between BCFss versus the membrane-water distribution coefficient (Dmw) and the protein-water partition coefficient (Kpw) of the studied perfluoroalkyl substances. However, BCFss exhibited a substantial drop for the very hydrophobic PFPiAs (C8/C10 and C6/C12 PFPiAs). The reduced BCFss of these long-chain PFPiAs (perfluoroalkyl chain length=18; Dmw=10(9)) is likely the result of reduced bioavailability due to interaction with solute molecules/organic matter present in the water phase and/or reduced gill membrane permeability. While PFPiAs can be metabolized to perfluoroalkyl phosphonic acids, the metabolic transformation rate seems insufficient to counteract the high degree of uptake across gill membranes. These findings help to better understand exposure pathways and bioaccumulation behavior of these important perfluorinated acids in aquatic systems.

  3. A review of the developments of multi-purpose primers and adhesives comprising novel dithiooctanoate monomers and phosphonic acid monomers.

    Science.gov (United States)

    Ikemura, Kunio; Endo, Takeshi; Kadoma, Yoshinori

    2012-02-03

    This paper reviews the developments of dithiooctanoate monomers and acidic adhesive monomers, and their roles in multi-purpose primers and adhesives in promoting adhesion to multiple substrate materials. Novel dithiooctanoate monomers exhibited excellent bonding to precious metals and alloys when compared against conventional sulfur-containing monomers. Newly developed phosphonic acid monomers, endowed with a water-soluble nature, enabled sufficient demineralization of dental hard tissues and thus improved bonding to both ground enamel and dentin. The optimal combination for bonding to dental hard tissues and precious and non-precious metals and alloys was 5.0 wt% 10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT) and 1.0 wt% 6-methacryloyloxyhexyl phosphonoacetate (6-MHPA). For bonding to dental porcelain, alumina, zirconia, and gold (Au) alloy, a ternary combination of silane coupling agent, acidic adhesive monomers, and dithiooctanoate monomers seemed promising. The latest development was a single-bottle, multi-purpose, self-etching adhesive which contained only acidic adhesive monomers and dithiooctanoate monomers but which produced strong adhesion to ground enamel and dentin, sandblasted zirconia, and Au alloy.

  4. Investigation of vinyl phosphonic acid/hydroxylated α-Al 2O 3( 0 0 0 1 ) reaction enthalpies

    Science.gov (United States)

    Hector, L. G., Jr.; Opalka, S. M.; Nitowski, G. A.; Wieserman, L.; Siegel, D. J.; Yu, H.; Adams, J. B.

    2001-11-01

    The eleven ion vinyl phosphonic acid (VPA) molecule consists of a phosphorus ion that serves as a cationic anchor for two electron-rich functional groups, viz., a tripodal oxygen-rich base and vinyl hydrocarbon tail. Recent inelastic tunneling experiments have implied that VPA binds in a tridentate coordination though its base leaving the vinyl tail free to react with a resin in adhesive bonding applications. Using first-principles total energy calculations, the reaction enthalpies for bonding of a single VPA molecule to selected threefold sites on hydroxylated α-Al 2O 3(0 0 0 1) are investigated. Tridentate, bidentate and unidentate coordinations, both with and without liberated water molecules, are examined to determine if the tridentate coordination is favored over the others and the extent to which the VPA molecule is sensitive to surface site geometry. The electron localization function is used to examine the extent of covalent character between the P-O bonds that anchor the VPA fragment to the oxide surface. Some comments on the entropic contributions of the VPA and H 2O molecules to the binding energetics are offered, along with a discussion of the effects of H 2O placement on the oxide surface and aluminum alloying agents.

  5. Structure-Property Relationship of Layered Metal Oxide Phosphonate/Chitosan Nanohybrids for Transducer in Biosensing Device

    Science.gov (United States)

    De, Sriparna; Mohanty, Smita; Nayak, Sanjay Kumar

    2015-01-01

    A candid approach to analyze the performance characteristics of phenyl phosphonate-functionalized zirconium oxide and pure zirconium oxide (ZrO2) fillers reinforced chitosan nanocomposites and their suitability as a potential biomaterial for the development of transducer surface in biosensing device has been investigated in this communication. Functionalization of ZrO2 has been carried out using sulfophenylphosphonate which was confirmed using Fourier transform infrared spectrographs. The electrostatic intercalation of chitosan with filler particles was monitored using electrochemical impedance analyzer which exhibits lowest bulk resistance which is highly effective for ionic switching. Incorporation of zirconium sulfophenylphosphonate (ZrSP) the ionic conductivity of the chitosan film attained a value of 1.2 × 10-6 S/cm as compared to the unmodified one which is a prefeasibility work for the fabrication of biosensing platform. Variation in performance characteristics has been evaluated through morphological and thermal characterization. TGA and DSC analysis reveal that the thermal stability and decomposition temperature of the nanocomposites were improved by the addition of reinforcing filler particles. XRD and SEM and TEM results support the above assumption. The continuous alignment of the proton transfer channels of the nanocomposites was thoroughly investigated by AFM analysis which revealed phase morphology for improved enzyme entrapment. Further, surface functionalized nanofillers result considerable increment of mechanical properties in terms of elastic modulus and tensile stress.

  6. Crystal structure, vibrational, spectral investigation, quantum chemical DFT calculations and thermal behavior of Diethyl [hydroxy (phenyl) methyl] phosphonate

    Science.gov (United States)

    Ouksel, Louiza; Chafaa, Salah; Bourzami, Riadh; Hamdouni, Noudjoud; Sebais, Miloud; Chafai, Nadjib

    2017-09-01

    Single Diethyl [hydroxy (phenyl) methyl] phosphonate (DHPMP) crystal with chemical formula C11H17O4P, was synthesized via the base-catalyzed Pudovik reaction and Lewis acid as catalyst. The results of SXRD analyzes indicate that this compound crystallizes into a mono-clinic system with space group P21/n symmetry and Z = 4. The crystal structure parameters are a = 9.293 Å, b = 8.103 Å, c = 17.542 Å, β = 95.329° and V = 1315.2 Å3, the structure displays one inter-molecular O-H⋯O hydrogen bonding. The UV-Visible absorption spectrum shows that the crystal exhibits a good optical transmission in the visible domain, and strong absorption in middle ultraviolet one. The vibrational frequencies of various functional groups present in DHPMP crystal have been deduced from FT-IR and FT-Raman spectra and then compared with theoretical values performed with DFT (B3LYP) method using 6-31G (p, d) basis sets. Chemical and thermodynamic parameters such as: ionization potential (I), electron affinity (A), hardness (σ), softness (η), electronegativity (χ) and electrophilicity index (ω), are also calculated using the same theoretical method. The thermal decomposition behavior of DHPMP, studied by using thermogravimetric analysis (TDG), shows a thermal stability until to 125 °C.

  7. New N-Acetyltransferase Fold in the Structure and Mechanism of the Phosphonate Biosynthetic Enzyme FrbF

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Brian; Cobb, Ryan E.; DeSieno, Matthew A.; Zhao, Huimin; Nair, Satish K. (UIUC)

    2015-10-15

    The enzyme FrbF from Streptomyces rubellomurinus has attracted significant attention due to its role in the biosynthesis of the antimalarial phosphonate FR-900098. The enzyme catalyzes acetyl transfer onto the hydroxamate of the FR-900098 precursors cytidine 5'-monophosphate-3-aminopropylphosphonate and cytidine 5'-monophosphate-N-hydroxy-3-aminopropylphosphonate. Despite the established function as a bona fide N-acetyltransferase, FrbF shows no sequence similarity to any member of the GCN5-like N-acetyltransferase (GNAT) superfamily. Here, we present the 2.0 {angstrom} resolution crystal structure of FrbF in complex with acetyl-CoA, which demonstrates a unique architecture that is distinct from those of canonical GNAT-like acetyltransferases. We also utilized the co-crystal structure to guide structure-function studies that identified the roles of putative active site residues in the acetyltransferase mechanism. The combined biochemical and structural analyses of FrbF provide insights into this previously uncharacterized family of N-acetyltransferases and also provide a molecular framework toward the production of novel N-acyl derivatives of FR-900098.

  8. Tribology and stability of organic monolayers on CrN: a comparison among silane, phosphonate, alkene, and alkyne chemistries.

    Science.gov (United States)

    Pujari, Sidharam P; Li, Yan; Regeling, Remco; Zuilhof, Han

    2013-08-20

    The fabrication of chemically and mechanically stable monolayers on the surfaces of various inorganic hard materials is crucial to the development of biomedical/electronic devices. In this Article, monolayers based on the reactivity of silane, phosphonate, 1-alkene, and 1-alkyne moieties were obtained on the hydroxyl-terminated chromium nitride surface. Their chemical stability and tribology were systematically investigated. The chemical stability of the modified CrN surfaces was tested in aqueous media at 60 °C at pH 3, 7, and 11 and monitored by static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), ellipsometry, and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). The tribological properties of the resulting organic monolayers with different end groups (fluorinated or nonfluorinated) were studied using atomic force microscopy (AFM). It was found that the fluorinated monolayers exhibit a dramatic reduction of adhesion and friction force as well as excellent wear resistance compared to those of nonfluorinated coatings and bare CrN substrates. The combination of remarkable chemical stability and superior tribological properties makes these fluorinated monolayers promising candidates for the development of robust high-performance devices.

  9. Anhydrous proton-conducting electrolyte membranes based on hyperbranched polymer with phosphonic acid groups for high-temperature fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Itoh, Takahito; Hirai, Keita; Tamura, Masashi; Uno, Takahiro; Kubo, Masataka [Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurima Machiya-cho, Tsu, Mie 514-8507 (Japan); Aihara, Yuichi [Samsung Yokohama Research Institute, 2-7 Sugasawa-cho, Tsurumi-ku, Yokohama 230-0027 (Japan)

    2008-04-01

    The two different molecular weight hyperbranched polymers (HBP(L)-PA-Ac and HBP(H)-PA-Ac) with both phosphonic acid group as a functional group and acryloyl group as a cross-linker at the chain ends were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked electrolyte membranes (CL-HBP-PA) were prepared by their thermal polymerizations using benzoyl peroxide and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the low molecular weight CL-HBP(L)-PA membrane and the high molecular weight CL-HBP(H)-PA membrane were found to be 1.2 x 10{sup -5} and 2.6 x 10{sup -6} S cm{sup -1}, respectively, at 150 C under dry condition, and showed the Vogel-Tamman-Fulcher (VTF) type temperature dependence. Both membranes were thermally stable up to 300 C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurements using a single membrane electrode assembly cell with both cross-linked membranes were successfully performed. (author)

  10. Phosphonate self-assembled monolayers as organic linkers in solid-state quantum dot sensetized solar cells

    KAUST Repository

    Ardalan, Pendar

    2010-06-01

    We have employed X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) spectroscopy, infrared (IR) spectroscopy, water contact angle (WCA) measurements, ellipsometry, and electrical measurements to study the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state quantum dot sensitized solar cells (QDSSCs). ∼2 to ∼6 nm size CdS quantum dots (QDs) were grown on the SAM-passivated TiO2 surfaces by successive ionic layer adsorption and reaction (SILAR). Our results show differences in the bonding of the CdS QDs at the TiO2 surfaces with a SAM linker. Moreover, our data indicate that presence of a SAM increases the CdS uptake on TiO2 as well as the performance of the resulting devices. Importantly, we observe ∼2 times higher power conversion efficiencies in the devices with a SAM compared to those that lack a SAM. © 2010 IEEE.

  11. Instructed neutralization, spontaneous neutralization and prevented neutralization after an obsession-like thought.

    NARCIS (Netherlands)

    M. van den Hout; M. Kindt; T. Weiland; M. Peters

    2002-01-01

    Building on 2 earlier experiments (S. Rachman et al [1996] and M. A. van den Hout [2001]) the present study investigated the effects of neutralizing the consequences of an obsession-like thought in healthy participants. Just like in the earlier studies, writing out and thinking of such a thought gen

  12. New Cleft-like Molecules and Macrocycles from Phosphonate Substituted Spirobisindanol

    Directory of Open Access Journals (Sweden)

    Paolo Finocchiaro

    2008-03-01

    Full Text Available We have synthetized medium-sized cyclophanes and macrocycles containingphosphonic groups, directly linked to the aromatic rings of the phanes or as pendant arms,for use as specific receptors for the selective complexation of neutral guests or forcomplexing lanthanides, as luminescent sensors and for diagnostic bioassays in medicine.Furthermore, because it would be of great interest for biochemistry as well as forpharmacological studies to dispose of preorganized rigid chiral hosts for biorelevantmolecules we designed inter alia, some new chiral macrocycles capable of a triple bindingmode and we used them for constructing macrocycles that could also be of interest forchiral recognition and chiral separations. Thus, in this paper we shall review the salientaspects of some macrocycles synthetized in our laboratory, all possessing the phosphonatemoiety and a spirobisindanol scaffold and able to act as complexing agents for cations andorganic substrates. In particular, we shall describe their NMR characterization, theirstereochemistry in solution and in the solid state, and their use as chiral receptors forbiorelevant molecules. Chiral HPLC resolution of some of them is also reported.

  13. Three new zinc(Ⅱ) coordination polymers: Modulation of extended structures driven by assistant ligands

    Institute of Scientific and Technical Information of China (English)

    DONG Zhe; ZHANG WeiHong; WANG YaoYu; LIU RuiTing; REN Chen; SHI QiZhen

    2009-01-01

    Three new complexes, [Zn(dtb)(4,4'-bipy)]·5H_2O (1), [Zn(dtb)(bpp)]·H_2O (2) and [Zn(dtb)(phen)_2].CH_3-propane, phen = 1,10-phenanthroline), have been constructed by dtb ligand and zinc salt in the pres-ence of different assistant N-containing ligands under hydrothermal conditions. The structures of the complexes were established by single-crystal X-ray diffraction analysis. Although compounds 1 and 2 are both 2D networks, the cavities' forms and pitch of helix are different. The structure of compound 3 shows a 1D helical chain, and is extended by the supermolecule interactions into a 2D framework. These neutral polymeric complexes exhibit structural and dimensional diversity due to the different coordination modes of the flexible dtb ligand and the effect of assistant ligands.

  14. Rocket Experiment For Neutral Upwelling

    Science.gov (United States)

    Kenward, D. R.; Lessard, M.

    2015-12-01

    Observations from the CHAMP satellite from 2004 show relatively small scale heating in the thermosphere. Several different mechanisms have been proposed to explain this phenomenon. The RENU 2 rocket mission includes a suite of 14 instruments which will acquire data to help understand processes involved in neutral upwelling in the cusp. Neutral, ion, and electron measurements will be made to provide an assessment of the upwelling process. SUPERDarn measurements of large- scale Joule heating in the cusp during overflight will also be acquired. Small-scale data which could possibly be associated with Alfvén waves, will be acquired using onboard electric field measurements. In-situ measurement of precipitating electrons and all other measurements will be used in thermodynamic and electrodynamic models for comparison to the observed upwelling.

  15. Optical Neutrality: Invisibility without Cloaking

    CERN Document Server

    Hodges, Reed; Durach, Maxim

    2016-01-01

    We show that it is possible to design an invisible wavelength-sized metal-dielectric metamaterial object without evoking cloaking. Our approach is an extension of the neutral inclusion concept by Zhou and Hu [Phys.Rev.E 74, 026607 (2006)] to Mie scatterers. We demonstrate that an increase of metal fraction in the metamaterial leads to a transition from dielectric-like to metal-like scattering, which proceeds through invisibility or optical neutrality of the scatterer. Formally this is due to cancellation of multiple scattering orders, similarly to plasmonic cloaking introduced by Alu and Engheta [Phys.Rev.E 72, 016623 (2005)], but without introduction of the separation of the scatterer into cloak and hidden regions.

  16. Neutral Hydrogen in Galaxy Groups

    CERN Document Server

    McKay, N P F; Brough, S; Forbes, D A; Barnes, D G

    2002-01-01

    We present preliminary results from a study of the neutral hydrogen (HI) properties of an X-ray selected sample of nearby loose galaxy groups. This forms part of a multi-wavelength investigation (X-ray, optical and radio) of the formation and evolution of galaxies within a group environment. Some initial findings of an ATNF Parkes Multibeam wide-area neutral hydrogen imaging survey of 17 nearby galaxy groups include two new, potentially isolated clouds of HI in the NGC 1052 and NGC 5044 groups and significant amounts of HI within the group virial radii of groups NGC 3557 and IC 1459 - two groups with complex X-ray structures that suggest they may still be in the act of virialisation. Here we present ATCA high-resolution synthesis-imaging follow-up observations of the distribution and kinematics of HI in these four groups.

  17. Neutrality and the social contract

    Directory of Open Access Journals (Sweden)

    Ian J. Carroll

    2009-06-01

    Full Text Available Given the fact of moral disagreement, theories of state neutrality which rely on moral premises will have limited application, in that they will fail to motivate anyone who rejects the moral premises on which they are based. By contrast, contractarian theories can be consistent with moral scepticism, and can therefore avoid this limitation. In this paper, I construct a contractarian model which I claim is sceptically consistent and includes a principle of state neutrality as a necessary condition. The principle of neutrality which I derive incorporates two conceptions of neutrality (consequential neutrality and justificatory neutrality which have usually been thought of as distinct and incompatible. I argue that contractarianism gives us a unified account of these conceptions. Ultimately, the conclusion that neutrality can be derived without violating the constraint established by moral scepticism turns out to rely on an assumption of equal precontractual bargaining power. I do not attempt to defend this assumption here. If the assumption cannot be defended in a sceptically consistent fashion, then the argument for neutrality given here is claimed to be morally minimal, rather than fully consistent with moral scepticism. L’existence d’un désaccord sur les questions morales fait en sorte que les constructions théoriques de la neutralité de l’État se fondant sur des prémisses morales ne peuvent avoir qu’une application limitée, car elles échouent à motiver quiconque rejette ces prémisses fondatrices. Par opposition, les théories contractualistes peuvent s’accommoder d’un scepticisme moral et peuvent donc éviter cette limitation. Cet article développe un modèle contractualiste compatible avec le scepticisme et qui inclut comme condition nécessaire la neutralité de l’État. Le principe de neutralité que je dérive à partir de ce modèle incorpore deux conceptions de la neutralité, soit la neutralité des cons

  18. Cyanomethylene-bis(phosphonate)-based lanthanide complexes: structural, photophysical, and magnetic investigations.

    Science.gov (United States)

    Maxim, Catalin; Branzea, Diana G; Tiseanu, Carmen; Rouzières, Mathieu; Clérac, Rodolphe; Andruh, Marius; Avarvari, Narcis

    2014-03-01

    The syntheses, structural investigations, magnetic and photophysical properties of a series of 10 lanthanide mononuclear complexes, containing the heteroditopic ligand cyanomethylene-bis(5,5-dimethyl-2-oxo-1,3,2λ(5)-dioxa-phosphorinane) (L), are described. The crystallographic analyses indicate two structural types: in the first one, [Ln(III)(L)3(H2O)2]·H2O (Ln = La, Pr, Nd), the metal ions are eight-coordinated within a square antiprism geometry, while the second one, [Ln(III)(L)3(H2O)]·8H2O (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er), contains seven-coordinated Ln(III) ions within distorted monocapped trigonal prisms. Intermolecular hydrogen bonding between nitrogen atoms of the cyano groups, crystallization, and coordination water molecules leads to the formation of extended supramolecular networks. Solid-state photophysical investigations demonstrate that Eu(III) and Tb(III) complexes possess intense luminescence with relatively long excited-state lifetimes of 530 and 1370 μs, respectively, while Pr(III), Dy(III), and Ho(III) complexes have weak intensity luminescence characterized by short lifetimes ranging between a few nanoseconds to microseconds. The magnetic properties for Pr(III), Gd(III), Tb(III), Dy(III), and Ho(III) complexes are in agreement with isolated Ln(III) ions in the solid state, as suggested by the single-crystal X-ray analyses. Alternating current (ac) susceptibility measurements up to 10 kHz reveal that only the Ho(III) complex shows a frequency-dependent ac response, with a relaxation mode clearly observed at 1.85 K around 4500 Hz.

  19. Optimization of Neutral Atom Imagers

    Science.gov (United States)

    Shappirio, M.; Coplan, M.; Balsamo, E.; Chornay, D.; Collier, M.; Hughes, P.; Keller, J.; Ogilvie, K.; Williams, E.

    2008-01-01

    The interactions between plasma structures and neutral atom populations in interplanetary space can be effectively studied with energetic neutral atom imagers. For neutral atoms with energies less than 1 keV, the most efficient detection method that preserves direction and energy information is conversion to negative ions on surfaces. We have examined a variety of surface materials and conversion geometries in order to identify the factors that determine conversion efficiency. For chemically and physically stable surfaces smoothness is of primary importance while properties such as work function have no obvious correlation to conversion efficiency. For the noble metals, tungsten, silicon, and graphite with comparable smoothness, conversion efficiency varies by a factor of two to three. We have also examined the way in which surface conversion efficiency varies with the angle of incidence of the neutral atom and have found that the highest efficiencies are obtained at angles of incidence greater then 80deg. The conversion efficiency of silicon, tungsten and graphite were examined most closely and the energy dependent variation of conversion efficiency measured over a range of incident angles. We have also developed methods for micromachining silicon in order to reduce the volume to surface area over that of a single flat surface and have been able to reduce volume to surface area ratios by up to a factor of 60. With smooth micro-machined surfaces of the optimum geometry, conversion efficiencies can be increased by an order of magnitude over instruments like LENA on the IMAGE spacecraft without increase the instruments mass or volume.

  20. Optimization of Neutral Atom Imagers

    Science.gov (United States)

    Shappirio, M.; Coplan, M.; Balsamo, E.; Chornay, D.; Collier, M.; Hughes, P.; Keller, J.; Ogilvie, K.; Williams, E.

    2008-01-01

    The interactions between plasma structures and neutral atom populations in interplanetary space can be effectively studied with energetic neutral atom imagers. For neutral atoms with energies less than 1 keV, the most efficient detection method that preserves direction and energy information is conversion to negative ions on surfaces. We have examined a variety of surface materials and conversion geometries in order to identify the factors that determine conversion efficiency. For chemically and physically stable surfaces smoothness is of primary importance while properties such as work function have no obvious correlation to conversion efficiency. For the noble metals, tungsten, silicon, and graphite with comparable smoothness, conversion efficiency varies by a factor of two to three. We have also examined the way in which surface conversion efficiency varies with the angle of incidence of the neutral atom and have found that the highest efficiencies are obtained at angles of incidence greater then 80deg. The conversion efficiency of silicon, tungsten and graphite were examined most closely and the energy dependent variation of conversion efficiency measured over a range of incident angles. We have also developed methods for micromachining silicon in order to reduce the volume to surface area over that of a single flat surface and have been able to reduce volume to surface area ratios by up to a factor of 60. With smooth micro-machined surfaces of the optimum geometry, conversion efficiencies can be increased by an order of magnitude over instruments like LENA on the IMAGE spacecraft without increase the instruments mass or volume.

  1. Neutral Naturalness with Bifundamental Gluinos

    CERN Document Server

    Gherghetta, Tony; Thomas, Zachary

    2016-01-01

    We study constraints on one-loop neutral naturalness at the LHC by considering gluon partners which are required to ameliorate the tuning in the Higgs mass-squared arising at two loops. This is done with a simple orbifold model of folded supersymmetry which not only contains color-neutral stops but also bifundamental gluinos that are charged under the Standard Model color group $SU(3)_C$ and a separate $SU(3)_C'$ group. The bifundamental gluinos reduce the Higgs mass tuning at two loops and maintain naturalness provided the gluinos are lighter than approximately 1.9 TeV for a 5 TeV cutoff scale. Limits from the LHC already forbid bifundamental gluinos below 1.4 TeV, and other non-colored states such as electroweakinos, $Z'$ bosons and dark sector bound states may be probed at future colliders. The search for bifundamental gluinos therefore provides a direct probe of one-loop neutral naturalness that can be fully explored at the LHC.

  2. Neutral naturalness with bifundamental gluinos

    Science.gov (United States)

    Gherghetta, Tony; Nguyen, Minh; Thomas, Zachary

    2016-12-01

    We study constraints on one-loop neutral naturalness at the LHC by considering gluon partners which are required to ameliorate the tuning in the Higgs mass-squared arising at two loops. This is done with a simple orbifold model of folded supersymmetry which not only contains color-neutral stops but also bifundamental gluinos that are charged under the Standard Model color group S U (3 )C and a separate S U (3 )C' group. The bifundamental gluinos reduce the Higgs mass tuning at two loops and maintain naturalness provided the gluinos are lighter than approximately 1.9 TeV for a 5 TeV cutoff scale. Limits from the LHC already forbid bifundamental gluinos below 1.4 TeV, and other noncolored states such as electroweakinos, Z' bosons and dark sector bound states may be probed at future colliders. The search for bifundamental gluinos therefore provides a direct probe of one-loop neutral naturalness that can be fully explored at the LHC.

  3. Types and Degrees of Vowel Neutrality

    National Research Council Canada - National Science Library

    Rebrus, Péter; Törkenczy, Miklós

    2016-01-01

    This paper argues that neutrality in a harmony system is a gradient property since it is due to a vowel's participation in different patterns that are considered to be indicators of neutral behaviour in harmony...

  4. Plasma/Neutral-Beam Etching Apparatus

    Science.gov (United States)

    Langer, William; Cohen, Samuel; Cuthbertson, John; Manos, Dennis; Motley, Robert

    1989-01-01

    Energies of neutral particles controllable. Apparatus developed to produce intense beams of reactant atoms for simulating low-Earth-orbit oxygen erosion, for studying beam-gas collisions, and for etching semiconductor substrates. Neutral beam formed by neutralization and reflection of accelerated plasma on metal plate. Plasma ejected from coaxial plasma gun toward neutralizing plate, where turned into beam of atoms or molecules and aimed at substrate to be etched.

  5. Plasma/Neutral-Beam Etching Apparatus

    Science.gov (United States)

    Langer, William; Cohen, Samuel; Cuthbertson, John; Manos, Dennis; Motley, Robert

    1989-01-01

    Energies of neutral particles controllable. Apparatus developed to produce intense beams of reactant atoms for simulating low-Earth-orbit oxygen erosion, for studying beam-gas collisions, and for etching semiconductor substrates. Neutral beam formed by neutralization and reflection of accelerated plasma on metal plate. Plasma ejected from coaxial plasma gun toward neutralizing plate, where turned into beam of atoms or molecules and aimed at substrate to be etched.

  6. Electroweak Chiral Lagrangian for Neutral Higgs Boson

    Institute of Scientific and Technical Information of China (English)

    WANG Shun-Zhi; WANG Qing

    2008-01-01

    A neutral Higgs boson is added into the traditional electroweak chiral Lagrangian by writing down all possible high dimension operators. The matter part of the Lagrangian is investigated in detail. We find that if Higgs field dependence of Yukawa couplings can be factorized out, there will be no flavour changing neutral couplings; neutral Higgs can induce coupling between light and heavy neutrinos.

  7. Lipophilicity determination of N-( benzothiazol-2-yl )-α-amino alkyl phosphonic diesters by RP-HPLC and RP-HPTLC

    Institute of Scientific and Technical Information of China (English)

    张玲; 李在国; 黄润秋; 王琴孙

    2000-01-01

    Using methanol-water mixtures as the mobile phase, the chromatographic retebtion parameters k' and R1 were determ1ined by reversed-phase high-perfor mance liquid chromatography (RP-HPLC) and reversed-phase high-performance thin-layer chromatograhy (RP-HPILC) for N-(benzothiazol-2-yl)-α-amino alkyl phosphonic diesters and the correlation with lipophilicity parameter (ClogP) was established. Logk wues obtained from RP-HPLC and Rmo values obtained from RP-HPTLC can be used to evaluate the lipophilicity of this kind of compounds. Chromatographic method is a good alternaive for lipophilicity measurement.

  8. Separation of lanthanum, hafnium, barium and radiotracers yttrium-88 and barium-133 using crystalline zirconium phosphate and phosphonate compounds as prospective materials for a Ra-223 radioisotope generator

    Energy Technology Data Exchange (ETDEWEB)

    Moeller, Teresia [Lynntech Inc., 7610 Eastmark Dr, College Station, TX 77840 (United States); Bestaoui, Naima, E-mail: Naima.Bestaoui@Lynntech.co [Lynntech Inc., 7610 Eastmark Dr, College Station, TX 77840 (United States); Wierzbicki, Melissa; Adams, Todd; Clearfield, Abraham [Lynntech Inc., 7610 Eastmark Dr, College Station, TX 77840 (United States)

    2011-07-15

    Crystalline hybrid organic/inorganic ion exchangers based on zirconium phosphate and phosphonate compounds were evaluated for application in radium-223 generator for radiopharmaceutical applications. Various compositions were synthesized and the selectivity of these materials was determined for inactive lanthanum, hafnium and barium, and radiotracers yttrium-88 and barium-133. The hybrid materials show very efficient lanthanum/barium separation; the response for zirconium phosphate was even better. A small-scale column loaded with pelletized zirconium phosphate compound demonstrated excellent retention of {sup 88}Y and release of {sup 133}Ba.

  9. Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in Metal-Ligand Complexes

    Institute of Scientific and Technical Information of China (English)

    Yong Ding; Jian-xiu Guo; Xiang-si Wang; Sha-sha Liu; Feng-cai Ma

    2009-01-01

    Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer (MLCT) in ruthenium(Ⅱ) ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os(bpy)(p0p)Cl ("Osp0p"; bpy=2,2'-bipyridyl; p0p=4,4'-bipyridyl) and the ligand-to-ligand charge transfer (LLCT) in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.

  10. Effects of increasing doses of samarium-153-ethylenediaminetetramethylene phosphonate on axial and appendicular skeletal growth in juvenile rabbits

    Energy Technology Data Exchange (ETDEWEB)

    Essman, Stephanie C. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)], E-mail: essmans@missouri.edu; Lewis, Michael R. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States); Department of Radiology, University of Missouri-Columbia, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri-Columbia, Columbia, MO 65211 (United States); Research Service, Harry S. Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Fox, Derek B. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)

    2008-02-15

    Introduction: Targeted radiotherapy using samarium-153-ethylenediaminetetramethylene phosphonate ({sup 153}Sm-EDTMP) is currently under investigation for treatment of osteosarcoma. Osteosarcoma often occurs in children, and previous studies on a juvenile rabbit model demonstrated that clinically significant damage to developing physeal cartilage may occur as a result of systemic {sup 153}Sm-EDTMP therapy. The aim of this study was to evaluate the late effects of {sup 153}Sm-EDTMP on skeletal structures during growth to maturity and to determine if there is a dose response of {sup 153}Sm-EDTMP on growth of long bones. Methods: Female 8-week-old New Zealand white rabbits were divided into three treatment groups plus controls. Each rabbit was intravenously administered a predetermined dose of {sup 153}Sm-EDTMP. Multiple bones of each rabbit were radiographed every 2 months until physeal closure, with subsequent measurements made to assess for abbreviated bone growth. Statistical analyses were performed to determine the differences in bone length between groups, with significance set at P<.05. Results: Significant differences in lengths of multiple bones were detected between the high-dose group and other treatment groups and controls at each time interval. A significant difference in lengths of the tibias was also noted in the medium-treatment group, compared to controls. Mean reduction of bone length was first detected at 4 months and did not increase significantly over time. Conclusions: These data suggest that clinically significant bone shortening may occur as a result of high-dosage administration of {sup 153}Sm-EDTMP. Further investigation regarding the effects of bone-seeking radiopharmaceuticals on bone growth and physeal cartilage is warranted.

  11. Recovery of phosphonate surface contaminants from glass using a simple vacuum extractor with a solid-phase microextraction fiber.

    Science.gov (United States)

    Groenewold, Gary S; Scott, Jill R; Rae, Catherine

    2011-07-04

    Recovery of chemical contaminants from fixed surfaces for analysis can be challenging, particularly if it is not possible to acquire a solid sample to be taken to the laboratory. A simple device is described that collects semi-volatile organic compounds from fixed surfaces by creating an enclosed volume over the surface, then generating a modest vacuum. A solid-phase microextraction (SPME) fiber is then inserted into the evacuated volume where it functions to sorb volatilized organic contaminants. The device is based on a syringe modified with a seal that is used to create the vacuum, with a perforable plunger through which the SPME fiber is inserted. The reduced pressure speeds partitioning of the semi-volatile compounds into the gas phase and reduces the boundary layer around the SPME fiber, which enables a fraction of the volatilized organics to partition into the SPME fiber. After sample collection, the SPME fiber is analyzed using conventional gas chromatography/mass spectrometry. The methodology has been used to collect organophosphorus compounds from glass surfaces, to provide a simple test for the functionality of the devices. Thirty minute sampling times (ΔT(vac)) resulted in fractional recovery efficiencies that ranged from 10(-3) to >10(-2), and in absolute terms, collection of low nanograms was demonstrated. Fractional recovery values were positively correlated to the vapor pressure of the compounds being sampled. Fractional recovery also increased with increasing ΔT(vac) and displayed a roughly logarithmic profile, indicating that an operational equilibrium is being approached. Fractional recovery decreased with increasing time between exposure and sampling; however, recordable quantities of the phosphonates could be collected three weeks after exposure.

  12. Surface coating from phosphonate ionic liquid electrolyte for the enhancement of the tribological performance of magnesium alloy.

    Science.gov (United States)

    Jiménez, Ana Eva; Rossi, Antonella; Fantauzzi, Marzia; Espinosa, Tulia; Arias-Pardilla, Joaquin; Martínez-Nicolás, Ginés; Bermúdez, María-Dolores

    2015-05-20

    A chronoamperometric method has been applied for the growth of a surface coating on AZ31B magnesium alloy, using the imidazolium alkylphosphonate room-temperature ionic liquid 1-ethyl-3-methylimidazolium ethylphosphonate ([EMIM][EtPO3H]) as electrolyte. A surface coating layer is obtained after 4 h under a constant voltage bias of -0.8 V with respect to the standard electrode. The coating nucleation and growth process correlates well with a 3D progressive mechanism. X-ray photoelectron spectrometry (XPS) analysis of [EMIM][EtPO3H] shows new P 2p and O 1s peaks after its use as electrolyte, as a consequence of reaction between the phosphonate anion and the magnesium substrate. Angle-resolved XPS (ARXPS) analysis of [EMIM][EtPO3H] did not show any change in the composition of the surface before and after chronoamperometry, since the sampling depth (1.5 nm at the highest emission angle) is larger than the cation and anion sizes (ca. 7 and 5 Å, respectively). Characterization of the coating was made by scanning electron microscopy (SEM), focussed ion beam SEM, energy dispersive X-ray spectroscopy, XPS, and ARXPS. FIB-SEM shows that the coating presents a mean thickness of 374 (±36) nm and contains magnesium and aluminum phosphates. Linear reciprocating tribological tests under variable load show that the presence of the coating can reduce friction coefficients of the coated AZ31B against steel up to 32% and wear rates up to 90%, with respect to the uncoated alloy.

  13. Estimation of apparent binding constant of complexes of selected acyclic nucleoside phosphonates with β-cyclodextrin by affinity capillary electrophoresis.

    Science.gov (United States)

    Šolínová, Veronika; Mikysková, Hana; Kaiser, Martin Maxmilián; Janeba, Zlatko; Holý, Antonín; Kašička, Václav

    2016-01-01

    Affinity capillary electrophoresis (ACE) has been applied to estimation of apparent binding constant of complexes of (R,S)-enantiomers of selected acyclic nucleoside phosphonates (ANPs) with chiral selector β-cyclodextrin (βCD) in aqueous alkaline medium. The noncovalent interactions of five pairs of (R,S)-enantiomers of ANPs-based antiviral drugs and their derivatives with βCD were investigated in the background electrolyte (BGE) composed of 35 or 50 mM sodium tetraborate, pH 10.0, and containing variable concentration (0-25 mM) of βCD. The apparent binding constants of the complexes of (R,S)-enantiomers of ANPs with βCD were estimated from the dependence of effective electrophoretic mobilities of (R,S)-enantiomers of ANPs (measured simultaneously by ACE at constant reference temperature 25°C inside the capillary) on the concentration of βCD in the BGE using different nonlinear and linear calculation methodologies. Nonlinear regression analysis provided more precise and accurate values of the binding constants and a higher correlation coefficient as compared to the regression analysis of the three linearized plots of the effective mobility dependence on βCD concentration in the BGE. The complexes of (R,S)-enantiomers of ANPs with βCD have been found to be relatively weak - their apparent binding constants determined by the nonlinear regression analysis were in the range 13.3-46.4 L/mol whereas the values from the linearized plots spanned the interval 12.3-55.2 L/mol.

  14. Automated facial coding software outperforms people in recognizing neutral faces as neutral from standardized datasets

    NARCIS (Netherlands)

    Lewinski, P.

    2015-01-01

    Little is known about people’s accuracy of recognizing neutral faces as neutral. In this paper, I demonstrate the importance of knowing how well people recognize neutral faces. I contrasted human recognition scores of 100 typical, neutral front-up facial images with scores of an arguably objective j

  15. ORNL positive ion neutral beam program

    Energy Technology Data Exchange (ETDEWEB)

    Whealton, J.H.; Haselton, H.H.; Barber, G.C.

    1978-01-01

    The neutral beam group at Oak Ridge National Laboratory has constructed neutral beam generators for the ORMAK and PLT devices, is presently constructing neutral beam devices for the ISX and PDX devices, and is contemplating the construction of neutral beam systems for the advanced TNS device. These neutral beam devices stem from the pioneering work on ion sources of G. G. Kelley and O. B. Morgan. We describe the ion sources under development at this Laboratory, the beam optics exhibited by these sources, as well as some theoretical considerations, and finally the remainder of the beamline design.

  16. Solvent-dependent switch of ligand donor ability and catalytic activity of ruthenium(II) complexes containing pyridinylidene amide (PYA) N-heterocyclic carbene hybrid ligands.

    Science.gov (United States)

    Leigh, Vivienne; Carleton, Daniel J; Olguin, Juan; Mueller-Bunz, Helge; Wright, L James; Albrecht, Martin

    2014-08-04

    Chelating ligands incorporating both N-[1-alkylpyridin-4(1H)-ylidene]amide (PYA) and N-heterocyclic carbene (NHC) donor sites were prepared and used for the synthesis of ruthenium(II) complexes. Cyclic voltammetry, NMR, and UV-vis spectroscopy of the complexes indicate a solvent-dependent contribution of the limiting resonance structures associated with the ligand in solution. The neutral pyridylidene imine structure is more pronounced in apolar solvents (CH2Cl2), while the mesoionic pyridinium amide form is predominant in polar solvents (MeOH, DMSO). The distinct electronic properties of these hybrid PYA-NHC ligands in different solvents have a direct influence on the catalytic activity of the ruthenium center, e.g., in the dehydrogenation of benzyl alcohol to benzaldehyde. The activity in different solvents qualitatively correlates with the solvent permittivity.

  17. Molecular Recognition and Ligand Association

    Science.gov (United States)

    Baron, Riccardo; McCammon, J. Andrew

    2013-04-01

    We review recent developments in our understanding of molecular recognition and ligand association, focusing on two major viewpoints: (a) studies that highlight new physical insight into the molecular recognition process and the driving forces determining thermodynamic signatures of binding and (b) recent methodological advances in applications to protein-ligand binding. In particular, we highlight the challenges posed by compensating enthalpic and entropic terms, competing solute and solvent contributions, and the relevance of complex configurational ensembles comprising multiple protein, ligand, and solvent intermediate states. As more complete physics is taken into account, computational approaches increase their ability to complement experimental measurements, by providing a microscopic, dynamic view of ensemble-averaged experimental observables. Physics-based approaches are increasingly expanding their power in pharmacology applications.

  18. Why mercury prefers soft ligands

    Energy Technology Data Exchange (ETDEWEB)

    Riccardi, Demian M [ORNL; Guo, Hao-Bo [ORNL; Gu, Baohua [ORNL; Parks, Jerry M [ORNL; Summers, Anne [University of Georgia, Athens, GA; Miller, S [University of California, San Francisco; Liang, Liyuan [ORNL; Smith, Jeremy C [ORNL

    2013-01-01

    Mercury (Hg) is a major global pollutant arising from both natural and anthropogenic sources. Defining the factors that determine the relative affinities of different ligands for the mercuric ion, Hg2+, is critical to understanding its speciation, transformation, and bioaccumulation in the environment. Here, we use quantum chemistry to dissect the relative binding free energies for a series of inorganic anion complexes of Hg2+. Comparison of Hg2+ ligand interactions in the gaseous and aqueous phases shows that differences in interactions with a few, local water molecules led to a clear periodic trend within the chalcogenide and halide groups and resulted in the well-known experimentally observed preference of Hg2+ for soft ligands such as thiols. Our approach establishes a basis for understanding Hg speciation in the biosphere.

  19. Activation of Aromatic C-C Bonds of 2,2'-Bipyridine Ligands.

    Science.gov (United States)

    Fombona, Sergio; Espinal-Viguri, Maialen; Huertos, Miguel A; Díaz, Jesús; López, Ramón; Menéndez, M Isabel; Pérez, Julio; Riera, Lucía

    2016-11-21

    4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo(II) and Re(I) cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

  20. High affinity ligands for 'diazepam-insensitive' benzodiazepine receptors.

    Science.gov (United States)

    Wong, G; Skolnick, P

    1992-01-14

    Structurally diverse compounds have been shown to possess high affinities for benzodiazepine receptors in their 'diazepam-sensitive' (DS) conformations. In contrast, only the imidazobenzodiazepinone Ro 15-4513 has been shown to exhibit a high affinity for the 'diazepam-insensitive' (DI) conformation of benzodiazepine receptors. We examined a series of 1,4-diazepines containing one or more annelated ring systems for their affinities at DI and DS benzodiazepine receptors, several 1,4-diazepinone carboxylates including Ro 19-4603, Ro 16-6028 and Ro 15-3505 were found to possess high affinities (Ki approximately 2.6-20 nM) for DI. Nonetheless, among the ligands examined, Ro 15-4513 was the only substance with a DI/DS potency ratio approximately 1; other substances had ratios ranging from 13 to greater than 1000. Ligands with high to moderate affinities at DI were previously classified as partial agonists, antagonists, or partial inverse agonists at DS benzodiazepine receptors, but behaved as 'GABA neutral' (antagonist) substances at DI. The identification of several additional high affinity ligands at DI benzodiazepine receptors may be helpful in elucidating the pharmacological and physiological importance of these sites.

  1. Monitoring Genomic Sequences during SELEX Using High-Throughput Sequencing: Neutral SELEX

    Science.gov (United States)

    Chen, Doris; Lorenz, Christina; Schroeder, Renée

    2010-01-01

    Background SELEX is a well established in vitro selection tool to analyze the structure of ligand-binding nucleic acid sequences called aptamers. Genomic SELEX transforms SELEX into a tool to discover novel, genomically encoded RNA or DNA sequences binding a ligand of interest, called genomic aptamers. Concerns have been raised regarding requirements imposed on RNA sequences undergoing SELEX selection. Methodology/Principal Findings To evaluate SELEX and assess the extent of these effects, we designed and performed a Neutral SELEX experiment omitting the selection step, such that the sequences are under the sole selective pressure of SELEX's amplification steps. Using high-throughput sequencing, we obtained thousands of full-length sequences from the initial genomic library and the pools after each of the 10 rounds of Neutral SELEX. We compared these to sequences obtained from a Genomic SELEX experiment deriving from the same initial library, but screening for RNAs binding with high affinity to the E. coli regulator protein Hfq. With each round of Neutral SELEX, sequences became less stable and changed in nucleotide content, but no sequences were enriched. In contrast, we detected substantial enrichment in the Hfq-selected set with enriched sequences having structural stability similar to the neutral sequences but with significantly different nucleotide selection. Conclusions/Significance Our data indicate that positive selection in SELEX acts independently of the neutral selective requirements imposed on the sequences. We conclude that Genomic SELEX, when combined with high-throughput sequencing of positively and neutrally selected pools, as well as the gnomic library, is a powerful method to identify genomic aptamers. PMID:20161784

  2. Monitoring genomic sequences during SELEX using high-throughput sequencing: neutral SELEX.

    Directory of Open Access Journals (Sweden)

    Bob Zimmermann

    Full Text Available BACKGROUND: SELEX is a well established in vitro selection tool to analyze the structure of ligand-binding nucleic acid sequences called aptamers. Genomic SELEX transforms SELEX into a tool to discover novel, genomically encoded RNA or DNA sequences binding a ligand of interest, called genomic aptamers. Concerns have been raised regarding requirements imposed on RNA sequences undergoing SELEX selection. METHODOLOGY/PRINCIPAL FINDINGS: To evaluate SELEX and assess the extent of these effects, we designed and performed a Neutral SELEX experiment omitting the selection step, such that the sequences are under the sole selective pressure of SELEX's amplification steps. Using high-throughput sequencing, we obtained thousands of full-length sequences from the initial genomic library and the pools after each of the 10 rounds of Neutral SELEX. We compared these to sequences obtained from a Genomic SELEX experiment deriving from the same initial library, but screening for RNAs binding with high affinity to the E. coli regulator protein Hfq. With each round of Neutral SELEX, sequences became less stable and changed in nucleotide content, but no sequences were enriched. In contrast, we detected substantial enrichment in the Hfq-selected set with enriched sequences having structural stability similar to the neutral sequences but with significantly different nucleotide selection. CONCLUSIONS/SIGNIFICANCE: Our data indicate that positive selection in SELEX acts independently of the neutral selective requirements imposed on the sequences. We conclude that Genomic SELEX, when combined with high-throughput sequencing of positively and neutrally selected pools, as well as the gnomic library, is a powerful method to identify genomic aptamers.

  3. Pitting corrosion of copper in aqueous solutions containing phosphonic acid as an inhibitor. Hosuhon san wo inhibita toshite fukumu suiyoekichu ni okeru do no koshiku ni tsuite

    Energy Technology Data Exchange (ETDEWEB)

    Yamada, Y. (Muroran Univ., Hokkaido (Japan). Graduate School); Seri, O.; Tagashira, K. (Muroran Univ., Hokkaido (Japan)); Nagata, K. (Sumitomo Light Metal Co. Ltd., Tokyo (Japan). Technical Research Lab.)

    1993-09-15

    Phosphonic acid-based inhibitors that are poured into cooling water for copper-tube circulation systems for open heat-accumulators were studied on their influence on pitting corrosion of copper. Amino trimethylene phosphonic acid (ATMP) dissolved into distilled water to 50 ppm was used for the immersion corrosion test. The corrosion-proof effect of additives such as ZnSO4, benzotriazole (BTA) was tested too. 0.5 mm thick phosphate-treated copper plates with a hole of 5 mm in diameter were used as test specimens. Pitting corrosion on the copper plate occurred when ATMP, BTA and ZnSO4 coexisted. It was proved that SO4 [sup 2-] is essential since Na2SO4 in stead of ZnSO4 induced also corrosion. The pitting took place when 0.6 ppm or more of SO4 [sup 2-] was present in a BTA-added ATMP solution. It was observed that the pitting is prone to occur with increase of SO4 [sup 2-] and the number of pitting increases. The following relationship is established when pitting corrosion occurs; E[sub b] [le] E[sub corr], where the former is a potential value at which current density shows a steep increase and the latter is an average value of spontaneous electrode potential showing a plateau. 8 refs., 11 figs., 1 tab.

  4. Catalytic synthesis of α-amino chromone phosphonates and their antimicrobial, toxicity and potential HIV-1 RT inhibitors based on silico screening.

    Science.gov (United States)

    Jaiyeola, Abosede Oluwabukola; Anand, K; Kasumbwe, K; Ramesh, M; Gengan, R M

    2017-01-01

    The α-amino phosphonates exhibit a wide range of biological properties which create demand for simple and efficient synthetic routes of new molecules. In this study synthesis of a new series of derivatives of α-amino chromone phosphonates (ACPs) was reported using RhBT catalyst. The RhBT was first prepared by simply mixing boron nitride in a solution of rhodium acetate, under inert atmosphere for a week followed by filtration (yield: 92%). The catalyst can be re-used for up to four times and showed minimal loss of activity. The ACPs was prepared in a one pot reaction containing chromone based aldehydes, aniline derivatives and diethyl phosphite. The structures of these compounds were characterized by IR, (1)H NMR, (13)C NMR, (31)P NMR and high resolution mass spectral analysis. The synthesized ACPs were evaluated for their antimicrobial activities against three bacteria B. cereus, M. luteus, E. coli and one fungus C. albicans. The ACPs displayed selective toxicity toward the brine shrimp (Artemia salina). Compounds 8j and 8m was found to be less toxic to the brine shrimp and may have more valuable biological application. Furthermore, molecular docking studies were conducted to predict the possible therapeutic potential of ACPs. The compounds (8i, 8j, 8k and 8m) were predicted as highly active HIV-1 reverse transcriptase inhibitors. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Comparison of silatrane, phosphonic acid, and carboxylic acid functional groups for attachment of porphyrin sensitizers to TiO2 in photoelectrochemical cells.

    Science.gov (United States)

    Brennan, Bradley J; Llansola Portolés, Manuel J; Liddell, Paul A; Moore, Thomas A; Moore, Ana L; Gust, Devens

    2013-10-21

    A tetra-arylporphyrin dye was functionalized with three different anchoring groups used to attach molecules to metal oxide surfaces. The physical, photophysical and electrochemical properties of the derivatized porphyrins were studied, and the dyes were then linked to mesoporous TiO2. The anchoring groups were β-vinyl groups bearing either a carboxylate, a phosphonate or a siloxy moiety. The siloxy linkages were made by treatment of the metal oxide with a silatrane derivative of the porphyrin. The surface binding and lability of the anchored molecules were studied, and dye performance was compared in a dye-sensitized solar cell (DSSC). Transient absorption spectroscopy was used to study charge recombination processes. At comparable surface concentration, the porphyrin showed comparable performance in the DSSC, regardless of the linker. However, the total surface coverage achievable with the carboxylate was about twice that obtainable with the other two linkers, and this led to higher current densities for the carboxylate DSSC. On the other hand, the carboxylate-linked dyes were readily leached from the metal oxide surface under alkaline conditions. The phosphonates were considerably less labile, and the siloxy-linked porphyrins were most resistant to leaching from the surface. The use of silatrane proved to be a practical and convenient way to introduce the siloxy linkages, which can confer greatly increased stability on dye-sensitized electrodes with photoelectrochemical performance comparable to that of the other linkers.

  6. A race for RAGE ligands.

    Science.gov (United States)

    Schleicher, Erwin D

    2010-08-01

    In experimental animals a causal involvement of the multiligand receptor for advanced glycation end products (RAGE) in the development of diabetic vascular complications has been demonstrated. However, the nature of RAGE ligands present in patients with diabetic nephropathy has not yet been defined; this leaves open the relevance of the RAGE system to the human disease.

  7. $\\tau$ decays with neutral kaons

    CERN Document Server

    Abbiendi, G.; Akesson, P.F.; Alexander, G.; Allison, John; Anderson, K.J.; Arcelli, S.; Asai, S.; Ashby, S.F.; Axen, D.; Azuelos, G.; Bailey, I.; Ball, A.H.; Barberio, E.; Barlow, Roger J.; Batley, J.R.; Baumann, S.; Behnke, T.; Bell, Kenneth Watson; Bella, G.; Bellerive, A.; Bentvelsen, S.; Bethke, S.; Betts, S.; Biebel, O.; Biguzzi, A.; Bloodworth, I.J.; Bock, P.; Bohme, J.; Boeriu, O.; Bonacorsi, D.; Boutemeur, M.; Braibant, S.; Bright-Thomas, P.; Brigliadori, L.; Brown, Robert M.; Burckhart, H.J.; Capiluppi, P.; Carnegie, R.K.; Carter, A.A.; Carter, J.R.; Chang, C.Y.; Charlton, David G.; Chrisman, D.; Ciocca, C.; Clarke, P.E.L.; Clay, E.; Cohen, I.; Conboy, J.E.; Cooke, O.C.; Couchman, J.; Couyoumtzelis, C.; Coxe, R.L.; Cuffiani, M.; Dado, S.; Dallavalle, G.Marco; Dallison, S.; Davis, R.; de Roeck, A.; Dervan, P.; Desch, K.; Dienes, B.; Dixit, M.S.; Donkers, M.; Dubbert, J.; Duchovni, E.; Duckeck, G.; Duerdoth, I.P.; Estabrooks, P.G.; Etzion, E.; Fabbri, F.; Fanfani, A.; Fanti, M.; Faust, A.A.; Feld, L.; Ferrari, P.; Fiedler, F.; Fierro, M.; Fleck, I.; Frey, A.; Furtjes, A.; Futyan, D.I.; Gagnon, P.; Gary, J.W.; Gaycken, G.; Geich-Gimbel, C.; Giacomelli, G.; Giacomelli, P.; Gingrich, D.M.; Glenzinski, D.; Goldberg, J.; Gorn, W.; Grandi, C.; Graham, K.; Gross, E.; Grunhaus, J.; Gruwe, M.; Hajdu, C.; Hanson, G.G.; Hansroul, M.; Hapke, M.; Harder, K.; Harel, A.; Hargrove, C.K.; Harin-Dirac, M.; Hauschild, M.; Hawkes, C.M.; Hawkings, R.; Hemingway, R.J.; Herten, G.; Heuer, R.D.; Hildreth, M.D.; Hill, J.C.; Hobson, P.R.; Hocker, James Andrew; Hoffman, Kara Dion; Homer, R.J.; Honma, A.K.; Horvath, D.; Hossain, K.R.; Howard, R.; Huntemeyer, P.; Igo-Kemenes, P.; Imrie, D.C.; Ishii, K.; Jacob, F.R.; Jawahery, A.; Jeremie, H.; Jimack, M.; Jones, C.R.; Jovanovic, P.; Junk, T.R.; Kanaya, N.; Kanzaki, J.; Karapetian, G.; Karlen, D.; Kartvelishvili, V.; Kawagoe, K.; Kawamoto, T.; Kayal, P.I.; Keeler, R.K.; Kellogg, R.G.; Kennedy, B.W.; Kim, D.H.; Klier, A.; Kobayashi, T.; Kobel, M.; Kokott, T.P.; Kolrep, M.; Komamiya, S.; Kowalewski, Robert V.; Kress, T.; Krieger, P.; von Krogh, J.; Kuhl, T.; Kupper, M.; Kyberd, P.; Lafferty, G.D.; Landsman, H.; Lanske, D.; Lauber, J.; Lawson, I.; Layter, J.G.; Lellouch, D.; Letts, J.; Levinson, L.; Liebisch, R.; Lillich, J.; List, B.; Littlewood, C.; Lloyd, A.W.; Lloyd, S.L.; Loebinger, F.K.; Long, G.D.; Losty, M.J.; Lu, J.; Ludwig, J.; Macchiolo, A.; Macpherson, A.; Mader, W.; Mannelli, M.; Marcellini, S.; Marchant, T.E.; Martin, A.J.; Martin, J.P.; Martinez, G.; Mashimo, T.; Mattig, Peter; McDonald, W.John; McKenna, J.; Mckigney, E.A.; McMahon, T.J.; McPherson, R.A.; Meijers, F.; Mendez-Lorenzo, P.; Merritt, F.S.; Mes, H.; Meyer, I.; Michelini, A.; Mihara, S.; Mikenberg, G.; Miller, D.J.; Mohr, W.; Montanari, A.; Mori, T.; Nagai, K.; Nakamura, I.; Neal, H.A.; Nisius, R.; O'Neale, S.W.; Oakham, F.G.; Odorici, F.; Ogren, H.O.; Okpara, A.; Oreglia, M.J.; Orito, S.; Pasztor, G.; Pater, J.R.; Patrick, G.N.; Patt, J.; Perez-Ochoa, R.; Petzold, S.; Pfeifenschneider, P.; Pilcher, J.E.; Pinfold, J.; Plane, David E.; Poli, B.; Polok, J.; Przybycien, M.; Quadt, A.; Rembser, C.; Rick, H.; Robins, S.A.; Rodning, N.; Roney, J.M.; Rosati, S.; Roscoe, K.; Rossi, A.M.; Rozen, Y.; Runge, K.; Runolfsson, O.; Rust, D.R.; Sachs, K.; Saeki, T.; Sahr, O.; Sang, W.M.; Sarkisian, E.K.G.; Sbarra, C.; Schaile, A.D.; Schaile, O.; Scharff-Hansen, P.; Schieck, J.; Schmitt, S.; Schoning, A.; Schroder, Matthias; Schumacher, M.; Schwick, C.; Scott, W.G.; Seuster, R.; Shears, T.G.; Shen, B.C.; Shepherd-Themistocleous, C.H.; Sherwood, P.; Siroli, G.P.; Skuja, A.; Smith, A.M.; Snow, G.A.; Sobie, R.; Soldner-Rembold, S.; Spagnolo, S.; Sproston, M.; Stahl, A.; Stephens, K.; Stoll, K.; Strom, David M.; Strohmer, R.; Surrow, B.; Talbot, S.D.; Taras, P.; Tarem, S.; Teuscher, R.; Thiergen, M.; Thomas, J.; Thomson, M.A.; Torrence, E.; Towers, S.; Trefzger, T.; Trigger, I.; Trocsanyi, Z.; Tsur, E.; Turner-Watson, M.F.; Ueda, I.; Van Kooten, Rick J.; Vannerem, P.; Verzocchi, M.; Voss, H.; Wackerle, F.; Waller, D.; Ward, C.P.; Ward, D.R.; Watkins, P.M.; Watson, A.T.; Watson, N.K.; Wells, P.S.; Wengler, T.; Wermes, N.; Wetterling, D.; White, J.S.; Wilson, G.W.; Wilson, J.A.; Wyatt, T.R.; Yamashita, S.; Zacek, V.; Zer-Zion, D.

    2000-01-01

    The branching ratio of the tau lepton to a neutral K meson is measured from a sample of approximately 200,000 tau decays recorded by the OPAL detector at centre-of-mass energies near the Z0 resonance. The measurement is based on two samples which identify one-prong tau decays with KL and KS mesons. The combined branching ratios are measured to be B(tau- -->pi- K0bar nutau) = (9.33+-0.68+-0.49)x10^-3 B(tau- -->pi- K0bar [>=1pi0] nutau) = (3.24+-0.74+-0.66)x10^-3 B(tau- -->K- K0bar [>=0pi0] nutau) = (3.30+-0.55+-0.39)x10^-3 where the first error is statistical and the second systematic.

  8. Laser sputter neutral mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    King, B.V.; Clarke, M.; Hu, H.; Betz [Newcastle Univ., NSW (Australia). Dept. of Physics

    1993-12-31

    Laser sputter neutral mass spectrometry (LSNMS) is an emerging technique for highly sensitive surface analysis. In this technique a target is bombarded with a pulsed beam of keV ions. The sputtered particles are intercepted by a high intensity pulsed laser beam above the surface and ionised with almost 100% efficiency. The photions may then be mass analysed using a quadrupole or, more commonly, using time of flight (TOF) techniques. In this method photoions are extracted from the ionisation region, accelerated to a known energy E{sub o} and strike a channelplate detector a distance `d` away. The flight time `t` of the photoions is then related to their mass by `d` {radical}m / {radical} 2E{sub o} so measurement of `t` allows mass spectra to be obtained. It is found that LSNMS is an emerging technique of great sensitivity and flexibility, useful for both applied analysis and to investigate basic sputtering processes. 4 refs., 3 figs.

  9. Increasing the Fill Factor of Inverted P3HT:PCBM Solar Cells Through Surface Modification of Al-Doped ZnO via Phosphonic Acid-Anchored C60 SAMs

    DEFF Research Database (Denmark)

    Stubhan, Tobias; Salinas, Michael; Ebel, Alexander

    2012-01-01

    The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene–SAMs leads to a reduction of the series resistance...

  10. Simultaneous enrichment of cysteine-containing peptides and phosphopeptides using a cysteine-specific phosphonate adaptable tag (CysPAT) in combination with titanium dioxide (TiO2) chromatography

    DEFF Research Database (Denmark)

    Huang, Honggang; Pedersen, Martin Haar; Ibañez-Vea, Maria

    2016-01-01

    Cysteine is a rare and conserved amino acid involved in most cellular functions. The thiol group of cysteine can be subjected to diverse oxidative modifications that regulate many physio-pathological states. In the present work, a Cysteine-specific Phosphonate Adaptable Tag (CysPAT) was synthesized...

  11. Genetic engineering of platelets to neutralize circulating tumor cells.

    Science.gov (United States)

    Li, Jiahe; Sharkey, Charles C; Wun, Brittany; Liesveld, Jane L; King, Michael R

    2016-04-28

    Mounting experimental evidence demonstrates that platelets support cancer metastasis. Within the circulatory system, platelets guard circulating tumor cells (CTCs) from immune elimination and promote their arrest at the endothelium, supporting CTC extravasation into secondary sites. Neutralization of CTCs in blood circulation can potentially attenuate metastases to distant organs. Therefore, extensive studies have explored the blockade of platelet-CTC interactions as an anti-metastatic strategy. Such an intervention approach, however, may cause bleeding disorders since the platelet-CTC interactions inherently rely on the blood coagulation cascade including platelet activation. On the other hand, platelets have been genetically engineered to correct inherited bleeding disorders in both animal models and human clinical trials. In this study, inspired by the physical association between platelets and CTCs, platelets were genetically modified to express surface-bound tumor necrosis factor-related apoptosis-inducing ligand (TRAIL), a cytokine known to induce apoptosis specifically in tumor cells. The TRAIL-expressing platelets were demonstrated to kill cancer cells in vitro and significantly reduce metastases in a mouse model of prostate cancer metastasis. Our results suggest that using platelets to produce and deliver cancer-specific therapeutics can provide a Trojan-horse strategy of neutralizing CTCs to attenuate metastasis.

  12. Primary neutral helium in the heliosphere

    CERN Document Server

    Mueller, Hans-Reinhard

    2012-01-01

    Two years of neutral measurements by IBEX-Lo have yielded several direct observations of interstellar neutral helium and oxygen during preferred viewing seasons. Besides the interstellar signal, there are indications of the presence of secondary neutral helium and oxygen created in the heliosphere. Detailed modeling of these particle species is necessary to connect the measured fluxes to the pristine local interstellar medium while accounting for loss and production of neutral particles during their path through the heliosphere. In this contribution, global heliosphere models are coupled to analytic calculations of neutral trajectories to obtain detailed estimates of the neutral distribution function of primary interstellar helium atoms in the heliosphere, in particular in the inner heliosphere.

  13. Molecular clock on a neutral network.

    Science.gov (United States)

    Raval, Alpan

    2007-09-28

    The number of fixed mutations accumulated in an evolving population often displays a variance that is significantly larger than the mean (the overdispersed molecular clock). By examining a generic evolutionary process on a neutral network of high-fitness genotypes, we establish a formalism for computing all cumulants of the full probability distribution of accumulated mutations in terms of graph properties of the neutral network, and use the formalism to prove overdispersion of the molecular clock. We further show that significant overdispersion arises naturally in evolution when the neutral network is highly sparse, exhibits large global fluctuations in neutrality, and small local fluctuations in neutrality. The results are also relevant for elucidating aspects of neutral network topology from empirical measurements of the substitution process.

  14. Antibody-ligand interactions for hydrophobic charge-induction chromatography: a surface plasmon resonance study.

    Science.gov (United States)

    Cheng, Fang; Li, Ming-Yang; Wang, Han-Qi; Lin, Dong-Qiang; Qu, Jing-Ping

    2015-03-24

    This article describes the use of surface plasmon resonance (SPR) spectroscopy to study antibody-ligand interactions for hydrophobic charge-induction chromatography (HCIC) and its versatility in investigating the surface and solution factors affecting the interactions. Two density model surfaces presenting the HCIC ligand (mercapto-ethyl-pyridine, MEP) were prepared on Au using a self-assembly technique. The surface chemistry and structure, ionization, and protein binding of such model surfaces were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), contact-angle titration, and SPR, respectively. The influences of the surface and solution factors, e.g., ligand density, salt concentration, and solution pH, on protein adsorption were determined by SPR. Our results showed that ligand density affects both equilibrium and dynamic aspects of the interactions. Specifically, a dense ligand leads to an increase in binding strength, rapid adsorption, slow desorption, and low specificity. In addition, both hydrophobic interactions and hydrogen bonding contribute significantly to the protein adsorption at neutral pH, while the electrostatic repulsion is overwhelmed under acidic conditions. The hydrophobic interaction at a high concentration of lyotropic salt would cause drastic conformational changes in the adsorbed protein. Combined with the self-assembly technique, SPR proves to be a powerful tool for studying the interactions between an antibody and a chromatographic ligand.

  15. Influenza virus antigenicity and broadly neutralizing epitopes.

    Science.gov (United States)

    Air, Gillian M

    2015-04-01

    A vaccine formulation that would be effective against all strains of influenza virus has long been a goal of vaccine developers, but antibodies after infection or vaccination were seen to be strain specific and there was little evidence of cross-reactive antibodies that neutralized across subtypes. Recently a number of broadly neutralizing monoclonal antibodies have been characterized. This review describes the different classes of broadly neutralizing antibodies and discusses the potential of their therapeutic use or for design of immunogens that induce a high proportion of broadly neutralizing antibodies.

  16. Alkaline solution neutralization capacity of soil.

    Science.gov (United States)

    Asakura, Hiroshi; Sakanakura, Hirofumi; Matsuto, Toshihiko

    2010-10-01

    Alkaline eluate from municipal solid waste (MSW) incineration residue deposited in landfill alkalizes waste and soil layers. From the viewpoint of accelerating stability and preventing heavy metal elution, pH of the landfill layer (waste and daily cover soil) should be controlled. On the other hand, pH of leachate from existing MSW landfill sites is usually approximately neutral. One of the reasons is that daily cover soil can neutralize alkaline solution containing Ca(2+) as cation. However, in landfill layer where various types of wastes and reactions should be taken into consideration, the ability to neutralize alkaline solutions other than Ca(OH)(2) by soil should be evaluated. In this study, the neutralization capacities of various types of soils were measured using Ca(OH)(2) and NaOH solutions. Each soil used in this study showed approximately the same capacity to neutralize both alkaline solutions of Ca(OH)(2) and NaOH. The cation exchange capacity was less than 30% of the maximum alkali neutralization capacity obtained by the titration test. The mechanism of neutralization by the pH-dependent charge can explain the same neutralization capacities of the soils. Although further investigation on the neutralization capacity of the soils for alkaline substances other than NaOH is required, daily cover soil could serve as a buffer zone for alkaline leachates containing Ca(OH)(2) or other alkaline substances.

  17. Microwave Diagnostics of Ultracold Neutral Plasma

    CERN Document Server

    Guo, Ronghua Lu Li

    2010-01-01

    We suggest an approach for using microwave radiation in diagnostics of ultracold neutral plasma. Microwave scattering from ultracold neutral plasma is calculated . Simple formulations are get and indicate that the dipole radiation power of ultracold neutral plasma does not depend on density profile $n_e(r)$ and $\\omega$ when $\\omega\\gg\\omega_{pe0}$, but on the total electron number $N_e$. This method provides the information of $N_e$ and from which we can get the three body recombination rate of the plasma, which is extremely important in the researches of ultracold neutral plasma.

  18. On implicit abstract neutral nonlinear differential equations

    Energy Technology Data Exchange (ETDEWEB)

    Hernández, Eduardo, E-mail: lalohm@ffclrp.usp.br [Universidade de São Paulo, Departamento de Computação e Matemática, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto (Brazil); O’Regan, Donal, E-mail: donal.oregan@nuigalway.ie [National University of Ireland, School of Mathematics, Statistics and Applied Mathematics (Ireland)

    2016-04-15

    In this paper we continue our developments in Hernández and O’Regan (J Funct Anal 261:3457–3481, 2011) on the existence of solutions for abstract neutral differential equations. In particular we extend the results in Hernández and O’Regan (J Funct Anal 261:3457–3481, 2011) for the case of implicit nonlinear neutral equations and we focus on applications to partial “nonlinear” neutral differential equations. Some applications involving partial neutral differential equations are presented.

  19. Iron-based magnetic superhalogens with pseudohalogens as ligands: An unbiased structure search

    Science.gov (United States)

    Ping Ding, Li; Shao, Peng; Lu, Cheng; Hui Zhang, Fang; Wang, Li Ya

    2017-01-01

    We have performed an unbiased structure search for a series of neutral and anionic FeL4 (L = BO2, CN, NO2, NO3, OH, CH3, NH2, BH4 and Li2H3) clusters using the CALYPSO (Crystal structure Analysis by Particle Swarm Optimization) structure search method. To probe the superhalogen properties of neutral and anionic FeL4 clusters, we used density-functional theory with the B3LYP functional to examine three factors, including distribution of extra electron, pattern of bonding and the nature of the ligands. Theoretical results show that Fe(BO2)4, Fe(NO3)4 and Fe(NO2)4 can be classified as magnetic superhalogen due to that their electron affinities even exceed those of the constituent ligands. The magnetic moment of Fe atom is almost entirly maintained when it is decorated with various ligands except for neutral and anionic (Li2H3)4. Moreover, the current work is also extended to the salt moieties formed by hyperhalogen/superhalogen anion and Na+ ion. It is found that these salts against dissociation into Na + FeL4 are thermodynamic stable except for Na[Fe(OH)4]. These results provides a wealth of electronic structure information about FeL4 magnetic superhalogens and offer insights into the synthesis mechanisms. PMID:28327547

  20. Liberal Neutrality : Constructivist, not foundationalist

    Directory of Open Access Journals (Sweden)

    Lendell Horne

    2009-06-01

    Full Text Available In defending the principle of neutrality, liberals have often appealed to a more general moral principle that forbids coercing persons in the name of reasons those persons themselves cannot reasonably be expected to share. Yet liberals have struggled to articulate a non-arbitrary, non-dogmatic distinction between the reasons that persons can reasonably be expected to share and those they cannot. The reason for this, I argue, is that what it means to “share a reason” is itself obscure. In this paper I articulate two different conceptions of what it is to share a reason; I call these conceptions “foundationalist” and “constructivist.” On the foundationalist view, two people “share” a reason just in the sense that the same reason applies to each of them independently. On this view, I argue, debates about the reasons we share collapse into debates about the reasons we have, moving us no closer to an adequate defense of neutrality. On the constructivist view, by contrast, “sharing reasons” is understood as a kind of activity, and the reasons we must share are just those reasons that make this activity possible. I argue that the constructivist conception of sharing reasons yields a better defense of the principle of neutrality. À travers leur défense du principe de neutralité, les libéraux ont souvent interpellé un principe moral plus général qui interdit de contraindre des personnes pour des raisons dont on ne peut raisonnablement attendre que ces personnes elles-mêmes les partagent. Les libéraux éprouvent cependant de la difficulté à articuler une distinction non-arbitraire et non-dogmatique entre les raisons dont on peut raisonnablement attendre que les personnes les partagent et celles dont on ne le peut pas. Je soutiens dans cet article que cette difficulté provient du fait que «partager une raison » est une notion obscure. Pour illustrer cela, je me pencherai sur deux conceptions distinctes de ce que veut dire

  1. Neutral Beams from Blazar Jets

    Science.gov (United States)

    Atoyan, Armen M.; Dermer, Charles D.

    2003-03-01

    We treat the production of neutrons, photons, and neutrinos through photomeson interactions of relativistic protons with ambient photons in the compact inner jets of blazars. Internal synchrotron and external isotropic radiation due to scattered optical/UV accretion-disk radiation are considered as target photon fields. Protons are assumed to be accelerated to a maximum energy limited by the size scale and magnetic field of the jet, and by competing energy losses. We characterize the conditions when the photomeson interactions of ultrarelativistic protons become effective, and show that the presence of the external radiation field makes possible strong energy losses for protons with energies Ep>~1015 eV. Without this component, effective energy losses of protons begin at Ep>~1018 eV, and would rapidly disappear with expansion of the blob. We develop a model describing the production and escape of neutrons from a comoving spherical blob, which continue to interact with the ambient external radiation field on the parsec-scale broad-line region (BLR). Neutrons may carry ~10% of the overall energy of the accelerated protons with Ep>~1015 eV outside the BLR. Ultra-high-energy gamma rays produced by photomeson interaction of neutrons outside the blob can also escape the BLR. The escaping neutrons, gamma rays, and neutrinos form a collimated neutral beam with a characteristic opening angle θ~1/Γ, where Γ is the bulk Lorentz factor of the inner jet. Energy and momentum is deposited in the extended jet from the decay of neutrons at distances ld(En)~(En/1017eV) kpc, and through pair-production attenuation of gamma rays with energies Eγ>~1015 eV which propagate to ~10-100 kpc distances. In this scenario, neutral beams of ultra-high-energy gamma rays and neutrons can be the reason for straight extended jets, such as in Pictor A. Fluxes of neutrinos detectable with kilometer-scale neutrino telescopes are predicted from flat-spectrum radio quasars such as 3C 279.

  2. Neutral and anionic superhalogen hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Swierszcz, Iwona [Department of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Anusiewicz, Iwona, E-mail: iwonaa@chem.univ.gda.pl [Department of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)

    2011-05-26

    Graphical abstract: The energy profile for the Na(OH){sub 2}{sup -} anionic hydroxide formation according to the NaOH+OH{sup -}{yields}Na(OH){sub 2}{sup -} reaction. Display Omitted Highlights: {yields} The superhalogen hydroxides and their anions were studied at the CCSD(T)/6-311++G(3df,3pd) level. {yields} All anionic superhalogen hydroxides were found to be thermodynamically stable. {yields} The VDE values calculated for the M(OH){sub k+1}{sup -} anions exceed 4 eV in all cases. {yields} The largest VDEs were found for the Al(OH){sub 4}{sup -} (6.07 eV) and Ga(OH){sub 4}{sup -} (6.21 eV). - Abstract: The properties of superhalogen M(OH){sub k+1}{sup -} anions and their M(OH){sub k+1} neutral parents (where M = Li, Na, K, Be, Mg, Ca, B, Al, Ga) were investigated at the ab initio CCSD(T)/6-311++G(3df,3pd)//MP2/6-311++G(d,p) level of theory. All the M(OH){sub k+1}{sup -} anions and some of their M(OH){sub k+1} neutral parents (k is the maximal formal valence of M) were found to be thermodynamically stable against the fragmentations (OH, OH{sup -}, O{sub 2} or H{sub 2}O loss). The vertical electron detachment energies (VDE) of the M(OH){sub k+1}{sup -} anions were calculated with the OVGF method and using the 6-311++G(3df,3pd) basis sets. The VDE values calculated for the anions studied exceed 4 eV in all cases, whereas the largest values of the electron binding energies were found for the Al(OH){sub 4}{sup -} (6.07 eV) and Ga(OH){sub 4}{sup -} anions (6.21 eV). Finally, formation of most of the species considered was predicted to be spontaneous due to the lack of kinetic barriers for these processes and their thermodynamic favorability.

  3. Quantum mechanical calculation of nanomaterial-ligand interaction energies by molecular fractionation with conjugated caps method

    Science.gov (United States)

    Zhang, Dawei

    2017-03-01

    Molecular fractionation with conjugate caps (MFCC) method is introduced for the efficient estimation of quantum mechanical (QM) interaction energies between nanomaterial (carbon nanotube, fullerene, and graphene surface) and ligand (charged and neutral). In the calculations, nanomaterials are partitioned into small fragments and conjugated caps that are properly capped, and the interaction energies can be obtained through the summation of QM calculations of the fragments from which the contribution of the conjugated caps is removed. All the calculations were performed by density functional theory (DFT) and dispersion contributions for the attractive interactions were investigated by dispersion corrected DFT method. The predicted interaction energies by MFCC at each computational level are found to give excellent agreement with full system (FS) calculations with the mean energy deviation just a fractional kcal/mol. The accurate determination of nanomaterial-ligand interaction energies by MFCC suggests that it is an effective method for performing QM calculations on nanomaterial-ligand systems.

  4. Quantum mechanical calculation of nanomaterial-ligand interaction energies by molecular fractionation with conjugated caps method

    Science.gov (United States)

    Zhang, Dawei

    2017-01-01

    Molecular fractionation with conjugate caps (MFCC) method is introduced for the efficient estimation of quantum mechanical (QM) interaction energies between nanomaterial (carbon nanotube, fullerene, and graphene surface) and ligand (charged and neutral). In the calculations, nanomaterials are partitioned into small fragments and conjugated caps that are properly capped, and the interaction energies can be obtained through the summation of QM calculations of the fragments from which the contribution of the conjugated caps is removed. All the calculations were performed by density functional theory (DFT) and dispersion contributions for the attractive interactions were investigated by dispersion corrected DFT method. The predicted interaction energies by MFCC at each computational level are found to give excellent agreement with full system (FS) calculations with the mean energy deviation just a fractional kcal/mol. The accurate determination of nanomaterial-ligand interaction energies by MFCC suggests that it is an effective method for performing QM calculations on nanomaterial-ligand systems. PMID:28300179

  5. Controlled-deactivation cannabinergic ligands.

    Science.gov (United States)

    Sharma, Rishi; Nikas, Spyros P; Paronis, Carol A; Wood, Jodianne T; Halikhedkar, Aneetha; Guo, Jason Jianxin; Thakur, Ganesh A; Kulkarni, Shashank; Benchama, Othman; Raghav, Jimit Girish; Gifford, Roger S; Järbe, Torbjörn U C; Bergman, Jack; Makriyannis, Alexandros

    2013-12-27

    We report an approach for obtaining novel cannabinoid analogues with controllable deactivation and improved druggability. Our design involves the incorporation of a metabolically labile ester group at the 2'-position on a series of (-)-Δ(8)-THC analogues. We have sought to introduce benzylic substituents α to the ester group which affect the half-lives of deactivation through enzymatic activity while enhancing the affinities and efficacies of individual ligands for the CB1 and CB2 receptors. The 1'-(S)-methyl, 1'-gem-dimethyl, and 1'-cyclobutyl analogues exhibit remarkably high affinities for both CB receptors. The novel ligands are susceptible to enzymatic hydrolysis by plasma esterases in a controllable manner, while their metabolites are inactive at the CB receptors. In further in vitro and in vivo experiments key analogues were shown to be potent CB1 receptor agonists and to exhibit CB1-mediated hypothermic and analgesic effects.

  6. Autologous HIV-1 neutralizing antibodies: emergence of neutralization-resistant escape virus and subsequent development of escape virus neutralizing antibodies

    DEFF Research Database (Denmark)

    Arendrup, M; Nielsen, C; Hansen, J E;

    1992-01-01

    The capacity of consecutive human sera to neutralize sequentially obtained autologous virus isolates was studied. HIV-1 was isolated three times over a 48-164-week period from three individuals immediately after seroconversion and from two individuals in later stages of infection. Development of ...... escape virus may be part of the explanation of the apparent failure of the immune system to control HIV infection.......The capacity of consecutive human sera to neutralize sequentially obtained autologous virus isolates was studied. HIV-1 was isolated three times over a 48-164-week period from three individuals immediately after seroconversion and from two individuals in later stages of infection. Development...... of neutralizing antibodies to the primary virus isolates was detected 13-45 weeks after seroconversion. Emergence of escape virus with reduced sensitivity to neutralization by autologous sera was demonstrated. The patients subsequently developed neutralizing antibodies against the escape virus but after a delay...

  7. 2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

    DEFF Research Database (Denmark)

    Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.;

    2005-01-01

    A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X......-ray structure of the dinuclear complex [{( Hbpbp) Fe(mu-OH)}(2)](ClO4)(4) center dot 2C(3)H(6)O ( 1 center dot 2C(3)H(6)O) shows that only one of the metal-binding cavities of each ligand is occupied by an iron( III) atom and two [Fe(Hbpbp)](3+) units are linked together by two hydroxo bridging groups to form...... bond lengths of the two different octahedral iron sites: Fe -mu-OH, 1.953( 5), 2.013( 5) angstrom and Fe-mu-O, 1.803( 5), 1.802( 5) angstrom. The difference in ligand environment is too small for allowing Mossbauer spectroscopy to distinguish between the two crystallographically independent Fe sites...

  8. Privileged chiral ligands and catalysts

    CERN Document Server

    Zhou, Qi-Lin

    2011-01-01

    This ultimate ""must have"" and long awaited reference for every chemist working in the field of asymmetric catalysis starts with the core structure of the catalysts, explaining why a certain ligand or catalyst is so successful. It describes in detail the history, the basic structural characteristics, and the applications of these ""privileged catalysts"". A novel concept that gives readers a much deeper insight into the topic.

  9. Tumor targeting via integrin ligands

    Directory of Open Access Journals (Sweden)

    Udaya Kiran eMarelli

    2013-08-01

    Full Text Available Selective and targeted delivery of drugs to tumors is a major challenge for an effective cancer therapy and also to overcome the side effects associated with current treatments. Overexpression of various receptors on tumor cells is a characteristic structural and biochemical aspect of tumors and distinguishes them from physiologically normal cells. This abnormal feature is therefore suitable for selectively directing anticancer molecules to tumors by using ligands that can preferentially recognize such receptors. Several subtypes of integrin receptors that are crucial for cell adhesion, cell signaling, cell viability and motility have been shown to have an upregulated expression on cancer cells. Thus, ligands that recognize specific integrin subtypes represent excellent candidates to be conjugated to drugs or drug carrier systems and be targeted to tumors. In this regard, integrins recognizing the RGD cell adhesive sequence have been extensively targeted for tumor specific drug delivery. Here we review key recent examples on the presentation of RGD-based integrin ligands by means of distinct drug delivery systems, and discuss the prospects of such therapies to specifically target tumor cells.

  10. Effective methylation of phosphonic acids related to chemical warfare agents mediated by trimethyloxonium tetrafluoroborate for their qualitative detection and identification by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Valdez, Carlos A; Leif, Roald N; Alcaraz, Armando

    2016-08-24

    The effective methylation of phosphonic acids related to chemical warfare agents (CWAs) employing trimethyloxonium tetrafluoroborate (TMO·BF4) for their qualitative detection and identification by gas chromatography-mass spectrometry (GC-MS) is presented. The methylation occurs in rapid fashion (1 h) and can be conveniently carried out at ambient temperature, thus providing a safer alternative to the universally employed diazomethane-based methylation protocols. Optimization of the methylation parameters led us to conclude that methylene chloride was the ideal solvent to carry out the derivatization, and that even though methylated products can be observed surfacing after only 1 h, additional time was not found to be detrimental but beneficial to the process particularly when dealing with analytes at low concentrations (∼10 μg mL(-1)). Due to its insolubility in methylene chloride, TMO·BF4 conveniently settles to the bottom during the reaction and does not produce additional interfering by-products that may further complicate the GC-MS analysis. The method was demonstrated to successfully methylate a variety of Schedule 2 phosphonic acids, including their half esters, resulting in derivatives that were readily detected and identified using the instrument's spectral library. Most importantly, the method was shown to simultaneously methylate a mixture of the organophosphorus-based nerve agent hydrolysis products: pinacolyl methylphosphonate (PMPA), cyclohexyl methylphosphonate (CyMPA) and ethyl methylphosphonate (EMPA) (at a 10 μg mL(-1) concentration each) in a fatty acid ester-rich organic matrix (OPCW-PT-O3) featured in the 38th Organisation for the Prohibition of Chemical Weapons (OPCW) Proficiency Test. In addition, the protocol was found to effectively methylate N,N-diethylamino ethanesulfonic acid and N,N-diisopropylamino ethanesulfonic acid that are products arising from the oxidative degradation of the V-series agents VR and VX respectively. The

  11. Which metabolic imaging, besides bone scan with 99mTc-phosphonates, for detecting and evaluating bone metastases in prostatic cancer patients? An open discussion.

    Science.gov (United States)

    Bombardieri, E; Setti, L; Kirienko, M; Antunovic, L; Guglielmo, P; Ciocia, G

    2015-12-01

    Prostate cancer bone metastases occur frequently in advanced cancer and this is matter of particular attention, due to the great impact on patient's management and considering that a lot of new emerging therapeutic options have been recently introduced. Imaging bone metastases is essential to localize lesions, to establish their size and number, to study characteristics and changes during therapy. Besides radiological imaging, nuclear medicine modalities can image their features and offer additional information about their metabolic behaviour. They can be classified according to physical characteristics, type of detection, mechanism of uptake, availability for daily use. The physiopathology of metastases formation and the mechanisms of tracer uptake are essential to understand the interpretation of nuclear medicine images. Therefore, radiopharmaceuticals for bone metastases can be classified in agents targeting bone (99mTc-phosphonates, 18F-fluoride) and those targeting prostatic cancer cells (18F-fluoromethylcholine, 11C-choline, 18F-fluorodeoxyglucose). The modalities using the first group of tracers are planar bone scan, SPECT or SPECT/CT with 99mTc-diphosphonates, and 18F-fluoride PET/CT, while the modalities using the second group include 18F/11C-choline derivatives PET/CT, 18F-FDG PET/CT and PET/CT scans with several other radiopharmaceuticals described in the literature, such as 18F/11C-acetate derivatives, 18F-fluoro-5α-dihydrotestosterone (FDHT), 18F-anti-1-amino-3-fluorocyclobutane-1-carboxylic acid (FACBC), 18F-2'-fluoro-5-methyl-1-β-D-arabinofuranosyluracil (FMAU) and 68Ga-labeled-prostate specific membrane antigen (PMSA) PET/TC. However, since data on clinical validation for these last novel modalities are not conclusive and/or are not still sufficient in number, at present they can be still considered as promising tools under evaluation. The present paper considers the nuclear modalities today available for the clinical routine. This overview wants

  12. Mechanisms of Hemagglutinin Targeted Influenza Virus Neutralization

    NARCIS (Netherlands)

    Brandenburg, Boerries; Koudstaal, Wouter; Goudsmit, Jaap; Klaren, Vincent; Tang, Chan; Bujny, Miriam V.; Korse, Hans J.W.M.; Kwaks, Ted; Otterstrom, Jason J.; Juraszek, Jarek; Oijen, Antoine M. van; Vogels, Ronald; Friesen, Robert H.E.

    2013-01-01

    Human monoclonal antibodies have been identified which neutralize broad spectra of influenza A or B viruses. Here, we dissect the mechanisms by which such antibodies interfere with infectivity. We distinguish four mechanisms that link the conserved hemagglutinin (HA) epitopes of broadly neutralizing

  13. 32 CFR 644.323 - Neutral language.

    Science.gov (United States)

    2010-07-01

    ... 32 National Defense 4 2010-07-01 2010-07-01 true Neutral language. 644.323 Section 644.323 National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY (CONTINUED) REAL PROPERTY REAL ESTATE HANDBOOK Disposal § 644.323 Neutral language. Wherever the words “man”, “men”, or their...

  14. "Unconventional" Neutralizing Activity of Antibodies Against HIV

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Neutralizing antibodies are recognized to be one of the essential elements of the adaptive immune response that must be induced by an effective vaccine against HIV. However, only a limited number of antibodies have been identified to neutralize a broad range of primary isolates of HIV-1 and attempts to induce such antibodies by immunization were unsuccessful. The difficulties to generate such antibodies are mainly due to intrinsic properties of HIV-1 envelope spikes, such as high sequence diversity, heavy glycosylation, and inducible and transient nature of certain epitopes. In vitro neutralizing antibodies are identified using "conventional" neutralization assay which uses phytohemagglutinin (PHA)-stimulated human PBMCs as target cells. Thus, in essence the assay evaluates HIV-1 replication in CD4+ T cells. Recently, several laboratories including us demonstrated that some monoclonal antibodies and HIV-1-specific polyclonal IgG purified from patient sera, although they do not have neutralizing activity when tested by the "conventional" neutralization assay, do exhibit potent and broad neutralizing activity in "unconventional" ways. The neutralizing activity of these antibodies and IgG fractions is acquired through post-translational modifications, through opsonization of virus particles into macrophages and immature dendritic cells (iDCs), or through expression of antibodies on the surface of HIV-1-susceptible cells. This review will focus on recent findings of this area and point out their potential applications in the development of preventive strategies against HIV.

  15. Ion-Neutral Coupling in Solar Prominences

    Science.gov (United States)

    Gilbert, Holly

    2011-01-01

    Interactions between ions and neutrals in a partially ionized plasma are important throughout heliophysics, including near the solar surface in prominences. Understanding how ion-neutral coupling affects formation, support, structure, and dynamics of prominences will advance our physical understanding of magnetized systems involving a transition from a weakly ionized dense gas to a fully ionized tenuous plasma. We address the fundamental physics of prominence support, which is normally described in terms of a magnetic force on the prominence plasma that balances the solar gravitational force, and the implications for observations. Because the prominence plasma is only partially ionized, it is necessary to consider the support of the both the ionized and neutral components. Support of the neutrals is accomplished through a frictional interaction between the neutral and ionized components of the plasma, and its efficacy depends strongly on the degree of ionization of the plasma. More specifically, the frictional force is proportional to the relative flow of neutral and ion species, and for a sufficiently weakly ionized plasma, this flow must be relatively large to produce a frictional force that balances gravity. A large relative flow, of course, implies significant draining of neutral particles from the prominence. We evaluate the importance of this draining effect for a hydrogen-helium plasma, and consider the observational evidence for cross-field diffusion of neutral prominence material.

  16. Topologies for neutral functional differential equations.

    Science.gov (United States)

    Melvin, W. R.

    1973-01-01

    Bounded topologies are considered for functional differential equations of the neutral type in which present dynamics of the system are influenced by its past behavior. A special bounded topology is generated on a collection of absolutely continuous functions with essentially bounded derivatives, and an application to a class of nonlinear neutral functional differential equations due to Driver (1965) is presented.

  17. Neutralizing antibodies in hepatitis C virus infection

    Institute of Scientific and Technical Information of China (English)

    Mirjam B Zeisel; Samira Fafi-Kremer; Isabel Fofana; Heidi Barth; Fran(c)oise Stoll-Keller; Michel Doffo(e)l; Thomas F Baumert

    2007-01-01

    Hepatitis C virus (HCV) is a major cause of hepatitis world-wide. The majority of infected individuals develop chronic hepatitis which can then progress to liver cirrhosis and hepatocellular carcinoma. Spontaneous viral clearance occurs in about 20%-30% of acutely infected individuals and results in resolution of infection without sequaelae. Both viral and host factors appear to play an important role for resolution of acute infection. A large body of evidence suggests that a strong, multispecific and long-lasting cellular immune response appears to be important for control of viral infection in acute hepatitis C. Due too the lack of convenient neutralization assays,the impact of neutralizing responses for control of viral infection had been less defined. In recent years, the development of robust tissue culture model systems for HCV entry and infection has finally allowed study of antibody-mediated neutralization and to gain further insights into viral targets of host neutralizing responses.In addition, detailed analysis of antibody-mediated neutralization in individual patients as well as cohorts with well defined viral isolates has enabled the study of neutralizing responses in the course of HCV infection and characterization of the impact of neutralizing antibodies for control of viral infection. This review will summarize recent progress in the understanding of the molecular mechanisms of antibody-mediated neutralization and its impact for HCV pathogenesis.(C) 2007 The WJG Press. All rights reserved.

  18. A neutral sampling formula for multiple samples and an 'exact' test of neutrality

    NARCIS (Netherlands)

    Etienne, Rampal S.

    2007-01-01

    As the utility of the neutral theory of biodiversity is increasingly being recognized, there is also an increasing need for proper tools to evaluate the relative importance of neutral processes (dispersal limitation and stochasticity). One of the key features of neutral theory is its close link to d

  19. A neutral sampling formula for multiple samples and an `exact' test of neutrality

    NARCIS (Netherlands)

    Etienne, R.S.

    2007-01-01

    As the utility of the neutral theory of biodiversity is increasingly being recognized, there is also an increasing need for proper tools to evaluate the relative importance of neutral processes (dispersal limitation and stochasticity). One of the key features of neutral theory is its close link to d

  20. Sensitive neutralization test for rubella antibody.

    Science.gov (United States)

    Sato, H; Albrecht, P; Krugman, S; Ennis, F A

    1979-01-01

    A modified rubella virus plaque neutralization test for measuring rubella antibody was developed based on the potentiation of the virus-antibody complex by heterologous anti-immunoglobulin. The test is highly sensitive, yielding titers on the average 50 to 100 times higher than the haemagglutination inhibition test or the conventional plaque neutralization test. The sensitivity of this enhanced neutralization test is somewhat limited by the existence of a prozone phenomenon which precludes testing of low-titered sera below a dilution of 1:16. No prozone effect was observed with cerebrospinal fluids. The specificity of the enhanced neutralization test was determined by seroconversion of individuals receiving rubella vaccine. Although the rubella hemagglutination inhibition test remains the test of choice in routine diagnostic and surveillance work, the enhanced rubella neutralization test is particularly useful in monitoring low-level antibody in the cerebrospinal fluid in patients with neurological disorders and in certain instances of vaccine failure. PMID:107192

  1. Shock acceleration in partially neutral plasmas

    CERN Document Server

    Morlino, G; Blasi, P; Caprioli, D

    2010-01-01

    We present the non-linear theory of shock acceleration applied to SNRs expanding into partially neutral plasma. Using this theory we show how the Balmer lines detected from young SNRs can be used to test the efficiency of shocks in the production of cosmic rays. In particular we investigate the effect of charge-exchange between protons and neutral hydrogen occurring in the precursor formed ahead of the shock. In this precursor the CR pressure accelerate the ionized component of the plasma and a relative velocity between protons and neutral hydrogen is established. On the other hand the charge-exchange process tends to equilibrate ions and neutrals resulting in the heating of both components. We show that even when the shock converts only a few per cent of the total bulk kinetic energy into CRs, the heating is efficient enough to produce a detectable broadening of the narrow Balmer lines emitted by the neutral hydrogen.

  2. Hydrolysis mechanism of anticancer drug lobaplatin in aqueous medium under neutral and acidic conditions: A DFT study

    Science.gov (United States)

    Reddy B., Venkata P.; Mukherjee, Subhajit; Mitra, Ishani; Mahata, Sujay; Linert, Wolfgang; Moi, Sankar Ch.

    2016-10-01

    We have studied the hydrolysis mechanism of lobaplatin in aqueous medium under neutral and acidic conditions using density functional theory combining with CPCM model. The stationary states located on potential energy surface were fully optimized and characterised. The rate limiting step in neutral conditions, ring opening reaction with an activation energy of 110.21 kJ mol-1. The completely hydrolysed complex is expected to be the reactive species towards the DNA purine bases. In acidic conditions, ligand detachment is the rate limiting step with an activation energy of 113.82 kJ mol-1. Consequently, monohydrated complex is expected to be the species reacting with DNA.

  3. Estimating the stoichiometry of HIV neutralization.

    Science.gov (United States)

    Magnus, Carsten; Regoes, Roland R

    2010-03-19

    HIV-1 virions infect target cells by first establishing contact between envelope glycoprotein trimers on the virion's surface and CD4 receptors on a target cell, recruiting co-receptors, fusing with the cell membrane and finally releasing the genetic material into the target cell. Specific experimental setups allow the study of the number of trimer-receptor-interactions needed for infection, i.e., the stoichiometry of entry and also the number of antibodies needed to prevent one trimer from engaging successfully in the entry process, i.e., the stoichiometry of (trimer) neutralization. Mathematical models are required to infer the stoichiometric parameters from these experimental data. Recently, we developed mathematical models for the estimations of the stoichiometry of entry [1]. In this article, we show how our models can be extended to investigate the stoichiometry of trimer neutralization. We study how various biological parameters affect the estimate of the stoichiometry of neutralization. We find that the distribution of trimer numbers-which is also an important determinant of the stoichiometry of entry-influences the estimated value of the stoichiometry of neutralization. In contrast, other parameters, which characterize the experimental system, diminish the information we can extract from the data about the stoichiometry of neutralization, and thus reduce our confidence in the estimate. We illustrate the use of our models by re-analyzing previously published data on the neutralization sensitivity [2], which contains measurements of neutralization sensitivity of viruses with different envelope proteins to antibodies with various specificities. Our mathematical framework represents the formal basis for the estimation of the stoichiometry of neutralization. Together with the stoichiometry of entry, the stoichiometry of trimer neutralization will allow one to calculate how many antibodies are required to neutralize a virion or even an entire population of

  4. Improvement of electrocatalytic performance of carbon supported Pd anodic catalyst in direct formic acid fuel cell by ethylenediamine-tetramethylene phosphonic acid

    Science.gov (United States)

    Lu, Liang; Li, Huanzhi; Hong, Yujie; Luo, Yafen; Tang, Yawen; Lu, Tianhong

    2012-07-01

    The direct formic acid fuel cell (DFAFC) has two major shortcomings that limit its lifespan and performance: (i) the poor electrocatalytic stability of the carbon supported Pd (Pd/C) catalyst for the oxidation of formic acid and (ii) rapid decomposition of formic acid over the Pd/C catalyst. To solve the problems, the Pd/C catalyst is modified with ethylenediamine-tetramethylene phosphonic acid (EDTMP). The resulting catalyst is designated as Pd/C-E catalyst. It is found that the Pd/C-E catalyst can inhibit the decomposition of formic acid and promote the oxidation of formic acid through the direct pathway. Consistently, the Pd/C-E catalyst is significantly protected from CO poisoning. As compared to the Pd/C catalyst, the electrocatalytic performance of the Pd/C-E catalyst is significantly superior. These results provide the first proof of the concept that DFAFC can be significantly improved by Pd/C-E catalyst.

  5. A mixed-valent uranium phosphonate framework containing U{sup IV}, U{sup V}, and U{sup VI}

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Lanhua; Zheng, Tao; Wang, Yaxing; Diwu, Juan; Chai, Zhifang; Wang, Shuao [School for Radiological and interdisciplinary Sciences (RAD-X), Soochow University, Suzhou (China); Collaborative Innovation Center of Radiation Medicine, Jiangsu Higher Education Institutions, Suzhou (China); Bao, Songsong; Zheng, Limin [State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University (China); Zhang, Linjuan; Wang, Jianqiang [Shanghai Institute of Applied Physics and, Key Laboratory of Nuclear Radiation and Nuclear Energy Technology, Chinese Academy of Sciences, Shanghai (China); Liu, Hsin-Kuan [Department of Chemistry, National Central University, Jhongli (China); Albrecht-Schmitt, Thomas E. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL (United States)

    2016-08-16

    It is shown that U{sup V}O{sub 2}{sup +} ions can reside at U{sup VI}O{sub 2}{sup 2+} lattice sites during mild reduction and crystallization process under solvothermal conditions, yielding a complicated and rare mixed-valent uranium phosphonate compound that simultaneously contains U{sup IV}, U{sup V}, and U{sup VI}. The presence of uranium with three oxidation states was confirmed by various characterization techniques, including X-ray crystallography, X-ray photoelectron, electron paramagnetic resonance, FTIR, UV/Vis-NIR absorption, and synchrotron radiation X-ray absorption spectroscopy, and magnetism measurements. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Efficacy of the acyclic nucleoside phosphonates (S)-9-(3-fluoro-2-phosphonylmethoxypropyl)adenine (FPMPA) and 9-(2-phosphonylmethoxyethyl)adenine (PMEA) against feline immunodeficiency virus.

    Science.gov (United States)

    Hartmann, K; Kuffer, M; Balzarini, J; Naesens, L; Goldberg, M; Erfle, V; Goebel, F D; De Clercq, E; Jindrich, J; Holy, A; Bischofberger, N; Kraft, W

    1998-02-01

    The acyclic nucleoside phosphonates (S)-9-(3-fluoro-2-phosphonylmethoxypropyl)adenine (FPMPA) and 9-(2-phosphonylmethoxyethyl)adenine (PMEA) were evaluated for their efficacy and side effects in a double-blind placebo-controlled trial using naturally occurring feline immunodeficiency virus (FIV)-infected cats. This natural retrovirus animal model is considered highly relevant for the pathogenesis and chemotherapy of HIV in humans. Both PMEA and FPMPA proved effective in ameliorating the clinical symptoms of FIV-infected cats, as measured by several clinical parameters including the incidence and severity of stomatitis, Karnofsky's score, immunologic parameters such as relative and absolute CD4+ lymphocyte counts, and virologic parameters including proviral DNA levels in peripheral blood mononuclear cells (PBMC) of drug-treated animals. In contrast with PMEA, FPMPA showed no hematologic side effects at a dose that was 2.5-fold higher than PMEA.

  7. Effect of phosphonate monolayer adsorbate on the microwave photoresponse of TiO2 nanotube membranes mounted on a planar double ring resonator

    Science.gov (United States)

    Zarifi, Mohammad H.; Farsinezhad, Samira; Wiltshire, Benjamin D.; Abdorrazaghi, Mohammad; Mahdi, Najia; Kar, Piyush; Daneshmand, Mojgan; Shankar, Karthik

    2016-09-01

    In this study, the effects of a phosphonate molecular monolayer adsorbed on the surface of a free-standing self-organized TiO2 nanotube membrane, on the microwave photoresponse of the membrane are presented. This phenomenon is monitored using planar microwave sensors. A double ring resonator is utilized to monitor the permittivity and conductivity variation on the monolayer coated membrane and the sensor environment separately. It is shown that the rise time and subsequent decay of the amplitude (A), resonance frequency (f 0) and quality factor (Q) of the resonator depend on the existence and the type of the monolayer coating the membrane. Three different monolayers of n-decylphosphonic acid (DPA), 1H, 1H‧, 2H, 2H‧-perfluorodecyl phosphonic acid (PFDPA) and 16-phosphonohexadecanoic acid adsorbed on the titania nanotube membrane are investigated while monitoring their microwave properties during the illumination time period and in the relaxation period, which demonstrate different behavior in comparison to each other and to the bare nanotube membrane layer. The effect of humidity on the TiO2 nanotube membrane with and without different monolayers is also studied and the results demonstrate distinguishable microwave responses. While each of the monolayer-coated membranes exhibited an attenuation of the photo-induced change in A, f 0 and Q with respect to the bare membrane, PFDPA-coated membranes showed the smallest relative change in the monitored microwave parameters upon ultraviolet illumination and upon the introduction of different levels of humidity. These effects are explained on the basis of surface trap passivation by the monolayers as well as the hydrophobicity of the monolayers. Our work also shows how the interactions of self-assembled monolayers with charge carriers and surface states on metal oxides may be used to indirectly sense their presence through measurement of the microwave response.

  8. Ligand placement based on prior structures: the guided ligand-replacement method

    Energy Technology Data Exchange (ETDEWEB)

    Klei, Herbert E. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Moriarty, Nigel W., E-mail: nwmoriarty@lbl.gov; Echols, Nathaniel [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Terwilliger, Thomas C. [Los Alamos National Laboratory, Los Alamos, NM 87545-0001 (United States); Baldwin, Eric T. [Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Natural Discovery LLC, Princeton, NJ 08542-0096 (United States); Pokross, Matt; Posy, Shana [Bristol-Myers Squibb, Princeton, NJ 08543-4000 (United States); Adams, Paul D. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); University of California at Berkeley, Berkeley, CA 94720-1762 (United States)

    2014-01-01

    A new module, Guided Ligand Replacement (GLR), has been developed in Phenix to increase the ease and success rate of ligand placement when prior protein-ligand complexes are available. The process of iterative structure-based drug design involves the X-ray crystal structure determination of upwards of 100 ligands with the same general scaffold (i.e. chemotype) complexed with very similar, if not identical, protein targets. In conjunction with insights from computational models and assays, this collection of crystal structures is analyzed to improve potency, to achieve better selectivity and to reduce liabilities such as absorption, distribution, metabolism, excretion and toxicology. Current methods for modeling ligands into electron-density maps typically do not utilize information on how similar ligands bound in related structures. Even if the electron density is of sufficient quality and resolution to allow de novo placement, the process can take considerable time as the size, complexity and torsional degrees of freedom of the ligands increase. A new module, Guided Ligand Replacement (GLR), was developed in Phenix to increase the ease and success rate of ligand placement when prior protein–ligand complexes are available. At the heart of GLR is an algorithm based on graph theory that associates atoms in the target ligand with analogous atoms in the reference ligand. Based on this correspondence, a set of coordinates is generated for the target ligand. GLR is especially useful in two situations: (i) modeling a series of large, flexible, complicated or macrocyclic ligands in successive structures and (ii) modeling ligands as part of a refinement pipeline that can automatically select a reference structure. Even in those cases for which no reference structure is available, if there are multiple copies of the bound ligand per asymmetric unit GLR offers an efficient way to complete the model after the first ligand has been placed. In all of these applications, GLR

  9. Net Neutrality: Media Discourses and Public Perception

    Directory of Open Access Journals (Sweden)

    Christine Quail

    2010-01-01

    Full Text Available This paper analyzes media and public discourses surrounding net neutrality, with particular attention to public utility philosophy, from a critical perspective. The article suggests that further public education about net neutrality would be beneficial. The first portion of this paper provides a survey of the existing literature surrounding net neutrality, highlighting the contentious debate between market-based and public interest perspectives. In order to contextualize the debate, an overview of public utility philosophy is provided, shedding light on how the Internet can be conceptualized as a public good. Following this discussion, an analysis of mainstream media is presented, exploring how the media represents the issue of net neutrality and whether or not the Internet is discussed through the lens of public utility. To further examine how the net neutrality debate is being addressed, and to see the potential impacts of media discourses on the general public, the results of a focus group are reported and analyzed. Finally, a discussion assesses the implications of the net neutrality debate as presented through media discourses, highlighting the future of net neutrality as an important policy issue.

  10. Neutral Supersymmetric Higgs Boson Searches

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Stephen Luke [Imperial College, London (United Kingdom)

    2008-07-01

    In some Supersymmetric extensions of the Standard Model, including the Minimal Supersymmetric Standard Model (MSSM), the coupling of Higgs bosons to b-quarks is enhanced. This enhancement makes the associated production of the Higgs with b-quarks an interesting search channel for the Higgs and Supersymmetry at D0. The identification of b-quarks, both online and offline, is essential to this search effort. This thesis describes the author's involvement in the development of both types of b-tagging and in the application of these techniques to the MSSM Higgs search. Work was carried out on the Level-3 trigger b-tagging algorithms. The impact parameter (IP) b-tagger was retuned and the effects of increased instantaneous luminosity on the tagger were studied. An extension of the IP-tagger to use the z-tracking information was developed. A new b-tagger using secondary vertices was developed and commissioned. A tool was developed to allow the use of large multi-run samples for trigger studies involving b-quarks. Offline, a neural network (NN) b-tagger was trained combining the existing offline lifetime based b-tagging tools. The efficiency and fake rate of the NN b-tagger were measured in data and MC. This b-tagger was internally reviewed and certified by the Collaboration and now provides the official b-tagging for all analyses using the Run IIa dataset at D0. A search was performed for neutral MSSM Higgs bosons decaying to a b{bar b} pair and produced in association with one or more b-quarks. Limits are set on the cross-section times the branching ratio for such a process. The limits were interpreted in various MSSM scenarios. This analysis uses the NN b-tagger and was the first to use this tool. The analysis also relies on triggers using the Level-3 IP b-tagging tool described previously. A likelihood discriminant was used to improve the analysis and a neural network was developed to cross-check this technique. The result of the analysis has been submitted to PRL

  11. Evaluation of smallpox vaccines using variola neutralization.

    Science.gov (United States)

    Damon, Inger K; Davidson, Whitni B; Hughes, Christine M; Olson, Victoria A; Smith, Scott K; Holman, Robert C; Frey, Sharon E; Newman, Frances; Belshe, Robert B; Yan, Lihan; Karem, Kevin

    2009-08-01

    The search for a 'third'-generation smallpox vaccine has resulted in the development and characterization of several vaccine candidates. A significant barrier to acceptance is the absence of challenge models showing induction of correlates of protective immunity against variola virus. In this light, virus neutralization provides one of few experimental methods to show specific 'in vitro' activity of vaccines against variola virus. Here, we provide characterization of the ability of a modified vaccinia virus Ankara vaccine to induce variola virus-neutralizing antibodies, and we provide comparison with the neutralization elicited by standard Dryvax vaccination.

  12. Beyond ITER: Neutral beams for DEMO

    CERN Document Server

    McAdams, R

    2013-01-01

    In the development of magnetically confined fusion as an economically sustainable power source, ITER is currently under construction. Beyond ITER is the DEMO programme in which the physics and engineering aspects of a future fusion power plant will be demonstrated. DEMO will produce net electrical power. The DEMO programme will be outlined and the role of neutral beams for heating and current drive will be described. In particular, the importance of the efficiency of neutral beam systems in terms of injected neutral beam power compared to wallplug power will be discussed. Options for improving this efficiency including advanced neutralisers and energy recovery are discussed.

  13. Synthesis, structural, thermal studies and biological activity of a tridentate Schiff base ligand and their transition metal complexes.

    Science.gov (United States)

    Abd El-halim, Hanan F; Omar, M M; Mohamed, Gehad G

    2011-01-01

    Schiff base (L) ligand is prepared via condensation of pyridine-2,6-dicarboxaldehyde with -2-aminopyridine. The ligand and its metal complexes are characterized based on elemental analysis, mass, IR, solid reflectance, magnetic moment, molar conductance, and thermal analyses (TG, DTG and DTA). The molar conductance reveals that all the metal chelates are non-electrolytes. IR spectra shows that L ligand behaves as neutral tridentate ligand and bind to the metal ions via the two azomethine N and pyridine N. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral (Cr(III), Fe(III), Co(II), Ni(II), Cu(II), and Th(IV)) and tetrahedral (Mn(II), Cd(II), Zn(II), and UO2(II)). The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DTG curves using Coats-Redfern method. The synthesized ligand, in comparison to their metal complexes also was screened for its antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data shows that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

  14. "Molecular Switches" on mGluR Allosteric Ligands That Modulate Modes of Pharmacology

    Science.gov (United States)

    Wood, Michael R.; Hopkins, Corey R.; Brogan, John T.; Conn, P. Jeffrey; Lindsley, Craig W.

    2013-01-01

    G-Protein-coupled receptors (GPCRs) represent the largest class of drug targets, accounting for more than 40% of marketed drugs; however, discovery efforts for many GPCRs have failed to provide viable drug candidates. Historically, drug discovery efforts have focused on developing ligands that act at the orthosteric site of the endogenous agonist. Recently, efforts have focused on functional assay paradigms and the discovery of ligands that act at allosteric sites to modulate receptor function in either a positive, negative, or neutral manner. Allosteric modulators have numerous advantages over orthosteric ligands, including high subtype selectivity; the ability to mimic physiological conditions; the lack of densensitization, downregulation, and internalization; and reduced side effects. Despite these virtues, challenging issues have now arisen for allosteric modulators of metabotropic glutamate receptors (mGluRs): shallow SAR, ligand-directed trafficking, and the identification of subtle “molecular switches” that modulate the modes of pharmacology. Here, we will discuss the impact of modest structural changes to multiple mGluR allosteric ligands scaffolds that unexpectedly modulate pharmacology and raise concerns over metabolism and the pharmacology of metabolites. PMID:21341760

  15. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.

    Science.gov (United States)

    Tong, Lianpeng; Inge, A Ken; Duan, Lele; Wang, Lei; Zou, Xiaodong; Sun, Licheng

    2013-03-04

    Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra.

  16. Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

    Directory of Open Access Journals (Sweden)

    Awatef Ayadi

    2015-08-01

    Full Text Available The synthesis and full characterization of two tetrathiafulvalene-appended azine ligands, namely 2-([2,2’-bi(1,3-dithiolylidene]-4-yl-6-((2,4-dinitrophenylhydrazonomethylpyridine (L1 and 5-([2,2’-bi(1,3-dithiolylidene]-4-yl-2-((2,4-dinitrophenylhydrazonomethylpyridine (L2 are described. The crystal structure of ligand L1 indicates that the ligand is completely planar with the presence of a strong intramolecular N3–H3···O1 hydrogen bonding. Titration experiments with inorganic anions showed that both ligands are suitable candidates for the sensing of fluoride anions. Ligand L2 was reacted with a Re(I cation to yield the corresponding rhenium tricarbonyl complex 3. In the crystal structure of the newly prepared electroactive rhenium complex the TTF is neutral and the rhenium cation is hexacoordinated. The electrochemical behavior of the three compounds indicates that they are promising for the construction of crystalline radical cation salts.

  17. Reactions of diiron m-aminocarbyne complexes containing nitrile ligands

    Directory of Open Access Journals (Sweden)

    Busetto Luigi

    2003-01-01

    Full Text Available The acetonitrile ligand in the mu-aminocarbyne complexes [Fe2{mu-CN(MeR}(mu-CO(CO(NCMe(Cp2][SO 3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c (Xyl = 2,6-Me2C6H3 is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe2{mu-CN(MeR}(mu-CO(CO(X(Cp2 ] (X = Br, I, CN. Complexes 2 undergo deprotonation and rearrangement of the coordinated MeCN upon treatment with organolithium reagents. Trimethylacetonitrile, that does not contain acidic alpha hydrogens has been used in place of MeCN to form the complexes [Fe2{mu-CN(MeR}(mu-CO(CO(NCCMe3 (Cp2][SO3CF3] (7a-c. Attempts to replace the nitrile ligand in 3 with carbon nucleophiles (by reaction with RLi failed, resulting in decomposition products. However the reaction of 7c with LiCºCTol (Tol = C6H4Me, followed by treatment with HSO3CF3, yielded the imino complex [Fe2{mu-CN(MeXyl}(mu-CO(CO {N(HC(CºCC6H4Me-4CMe3}(Cp 2][SO3CF3 ] (8, obtained via acetilyde addition at the coordinated NCCMe3.

  18. CB receptor ligands from plants.

    Science.gov (United States)

    Woelkart, Karin; Salo-Ahen, Outi M H; Bauer, Rudolf

    2008-01-01

    Advances in understanding the physiology and pharmacology of the endogenous cannabinoid system have potentiated the interest of cannabinoid receptors as potential therapeutic targets. Cannabinoids have been shown to modulate a variety of immune cell functions and have therapeutic implications on central nervous system (CNS) inflammation, chronic inflammatory conditions such as arthritis, and may be therapeutically useful in treating autoimmune conditions such as multiple sclerosis. Many of these drug effects occur through cannabinoid receptor signalling mechanisms and the modulation of cytokines and other gene products. Further, endocannabinoids have been found to have many physiological and patho-physiological functions, including mood alteration and analgesia, control of energy balance, gut motility, motor and co-ordination activities, as well as alleviation of neurological, psychiatric and eating disorders. Plants offer a wide range of chemical diversity and have been a growing domain in the search for effective cannabinoid ligands. Cannabis sativa L. with the known plant cannabinoid, Delta(9-)tetrahydrocannabinol (THC) and Echinacea species with the cannabinoid (CB) receptor-binding lipophilic alkamides are the best known herbal cannabimimetics. This review focuses on the state of the art in CB ligands from plants, as well their possible therapeutic and immunomodulatory effects.

  19. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  20. Measurement of protein-ligand complex formation.

    Science.gov (United States)

    Lowe, Peter N; Vaughan, Cara K; Daviter, Tina

    2013-01-01

    Experimental approaches to detect, measure, and quantify protein-ligand binding, along with their theoretical bases, are described. A range of methods for detection of protein-ligand interactions is summarized. Specific protocols are provided for a nonequilibrium procedure pull-down assay, for an equilibrium direct binding method and its modification into a competition-based measurement and for steady-state measurements based on the effects of ligands on enzyme catalysis.

  1. Neutral Aggregation in Finite Length Genotype space

    CERN Document Server

    Houchmandzadeh, Bahram

    2016-01-01

    The advent of modern genome sequencing techniques allows for a more stringent test of the neutrality hypothesis of Evolution, where all individuals have the same fitness. Using the individual based model of Wright and Fisher, we compute the amplitude of neutral aggregation in the genome space, i.e., the probability PL,$\\Theta$,M (k) of finding two individuals at genetic distance k for a genome of size L and mutation and migration number $\\Theta$ and M. In well mixed populations, we show that for $\\Theta$ $\\ll$ L, neutral aggregation is the dominant force and most individuals are found at short genetic distances from each other. For $\\Theta$ $\\sim$ L/2 on the contrary, individuals are randomly dispersed in genome space. For a geographically dispersed population, the controlling parameter is a combination of mutation and migration numbers. The theory we develop can be used to test the neutrality hypothesis in various ecological and evolutionary systems.

  2. Roles for ordered and bulk solvent in ligand recognition and docking in two related cavities.

    Directory of Open Access Journals (Sweden)

    Sarah Barelier

    Full Text Available A key challenge in structure-based discovery is accounting for modulation of protein-ligand interactions by ordered and bulk solvent. To investigate this, we compared ligand binding to a buried cavity in Cytochrome c Peroxidase (CcP, where affinity is dominated by a single ionic interaction, versus a cavity variant partly opened to solvent by loop deletion. This opening had unexpected effects on ligand orientation, affinity, and ordered water structure. Some ligands lost over ten-fold in affinity and reoriented in the cavity, while others retained their geometries, formed new interactions with water networks, and improved affinity. To test our ability to discover new ligands against this opened site prospectively, a 534,000 fragment library was docked against the open cavity using two models of ligand solvation. Using an older solvation model that prioritized many neutral molecules, three such uncharged docking hits were tested, none of which was observed to bind; these molecules were not highly ranked by the new, context-dependent solvation score. Using this new method, another 15 highly-ranked molecules were tested for binding. In contrast to the previous result, 14 of these bound detectably, with affinities ranging from 8 µM to 2 mM. In crystal structures, four of these new ligands superposed well with the docking predictions but two did not, reflecting unanticipated interactions with newly ordered waters molecules. Comparing recognition between this open cavity and its buried analog begins to isolate the roles of ordered solvent in a system that lends itself readily to prospective testing and that may be broadly useful to the community.

  3. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    Directory of Open Access Journals (Sweden)

    Antonio Monopoli

    2015-06-01

    Full Text Available The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

  4. Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

    KAUST Repository

    Veenboer, Richard M. P.

    2017-09-08

    The synthesis and isolation of gold(I) precatalysts often requires the generation of several isolable intermediates as well as numerous purification steps. New protocols for the expedient synthesis of neutral [Au(OH)(NHC)] and [Au(CH2COCH3)(NHC)] species from [AuCl(NHC)] or [AuCl(DMS)] precursors bearing a variety of N-heterocyclic carbene (NHC) ligands are presented. These methods can be employed in a telescoping manner for the synthesis of catalytically relevant [Au(NTf2)(NHC)] and [Au(NHC)(NCCH3)][BF4] complexes. These attractive methods are straightforward and practical leading to various complexes in high isolated yields and purity.

  5. Neutral thermospheric temperature from ion concentration measurements

    Science.gov (United States)

    Breig, E. L.; Donaldson, J. S.; Hanson, W. B.; Hoffman, J. H.; Power, R. A.; Kayser, D. C.; Spencer, N. W.; Wharton, L. E.

    1981-01-01

    A technique for extracting information on neutral temperature from in situ F region measurements of O(+) and H(+) ion concentrations is analyzed and evaluated. Advantage is taken of the condition of charge-exchange equilibrium of these species in the neighborhood of 320 km to infer the associated relative abundances of neutral oxygen and hydrogen. Results are shown to be generally consistent with other concurrent in situ measurements.

  6. The Framing of Network Neutrality Governance

    DEFF Research Database (Denmark)

    Perry, James

    The neutrality of the internet with regard to applications (e.g. search, social networking, email, to mention only three) has been central to innovation and growth in the knowledge-economy over the past two decades. Until recently, neutrality was built into the internet's design via its core stan...... with a critical analysis of their respective operational paradigms, the paper seeks to understand who is framing the debate, how they are doing so, and to what (systemic) effect....

  7. Γ-source Neutral Point Clamped Inverter

    DEFF Research Database (Denmark)

    Mo, Wei; Loh, Poh Chiang; Blaabjerg, Frede

    Transformer based Z-source inverters are recently proposed to achieve promising buck-boost capability. They have improved higher buck-boost capability, smaller size and less components count over Z-source inverters. On the other hand, neutral point clamped inverters have less switching stress...... and better output performance comparing with traditional two-level inverters. Integrating these two types of configurations can help neutral point inverters achieve enhanced votlage buck-boost capability....

  8. ITER neutral beam system US conceptual design

    Energy Technology Data Exchange (ETDEWEB)

    Purgalis, P.

    1990-09-01

    In this document we present the US conceptual design of a neutral beam system for International Thermonuclear Experimental Reactor (ITER). The design incorporates a barium surface conversion D{sup {minus}} source feeding a linear array of accelerator channels. The system uses a dc accelerator with electrostatic quadrupoles for strong focusing. A high voltage power supply that is integrated with the accelerator is presented as an attractive option. A gas neutralizer is used and residual ions exiting the neutralizer are deflected to water-cooled dumps. Cryopanels are located at the accelerator exit to pump excess gas from the source and the neutralizer, and in the ion dump cavity to pump re-neutralized ions and neutralizer gas. All the above components are packaged in compact identical, independent modules which can be removed for remote maintenance. The neutral beam system delivers 75 MW of DO at 1.3 MeV, into three ports with a total of 9 modules arranged in stacks of three modules per port . To increase reliability each module is designed to deliver up to 10 MW; this allows eight modules operating at partial capacity to deliver the required power in the event one module is out of service, and provides 20% excess capacity to improve availability. Radiation protection is provided by shielding and by locating critical components in the source and accelerator 46.5 m from the torus centerline. Neutron shielding in the drift duct and neutralizer provides the added feature of limiting conductance and thus reducing gas flow to and from the torus.

  9. Nitrogen-neutrality: a step towards sustainability

    Science.gov (United States)

    Leip, Adrian; Leach, Allison; Musinguzi, Patrick; Tumwesigye, Trust; Olupot, Giregon; Tenywa, John Stephen; Mudiope, Joseph; Hutton, Olivia; Cordovil, Claudia M. d. S.; Bekunda, Mateete; Galloway, James

    2014-11-01

    We propose a novel indicator measuring one dimension of the sustainability of an entity in modern societies: Nitrogen-neutrality. N-neutrality strives to offset Nr releases an entity exerts on the environment from the release of reactive nitrogen (Nr) to the environment by reducing it and by offsetting the Nr releases elsewhere. N-neutrality also aims to increase awareness about the consequences of unintentional releases of nitrogen to the environment. N-neutrality is composed of two quantified elements: Nr released by an entity (e.g. on the basis of the N footprint) and Nr reduction from management and offset projects (N offset). It includes management strategies to reduce nitrogen losses before they occur (e.g., through energy conservation). Each of those elements faces specific challenges with regard to data availability and conceptual development. Impacts of Nr releases to the environment are manifold, and the impact profile of one unit of Nr release depends strongly on the compound released and the local susceptibility to Nr. As such, N-neutrality is more difficult to conceptualize and calculate than C-neutrality. We developed a workable conceptual framework for N-neutrality which was adapted for the 6th International Nitrogen Conference (N2013, Kampala, November 2013). Total N footprint of the surveyed meals at N2013 was 66 kg N. A total of US 3050 was collected from the participants and used to offset the conference’s N footprint by supporting the UN Millennium Village cluster Ruhiira in South-Western Uganda. The concept needs further development in particular to better incorporate the spatio-temporal variability of impacts and to standardize the methods to quantify the required N offset to neutralize the Nr releases impact. Criteria for compensation projects need to be sharply defined to allow the development of a market for N offset certificates.

  10. Neutral particle kinetics in fusion devices

    Energy Technology Data Exchange (ETDEWEB)

    Tendler, M.; Heifetz, D.

    1986-05-01

    The theory of neutral particle kinetics treats the transport of mass, momentum, and energy in a plasma due to neutral particles which themselves are unaffected by magnetic fields. This transport affects the global power and particle balances in fusion devices, as well as profile control and plasma confinement quality, particle and energy fluxes onto device components, performance of pumping systems, and the design of diagnostics and the interpretation of their measurements. This paper reviews the development of analytic, numerical, and Monte Carlo methods of solving the time-independent Boltzmann equation describing neutral kinetics. These models for neutral particle behavior typically use adaptations of techniques developed originally for computing neutron transport, due to the analogy between the two phenomena, where charge-exchange corresponds to scattering and ionization to absorption. Progress in the field depends on developing multidimensional analytic methods, and obtaining experimental data for the physical processes of wall reflection, the neutral/plasma interaction, and for processes in fusion devices which are directly related to neutral transport, such as H/sub ..cap alpha../ emission rates, plenum pressures, and charge-exchange emission spectra.

  11. Automated Facial Coding Software Outperforms People in Recognizing Neutral Faces as Neutral from Standardized Datasets

    Directory of Open Access Journals (Sweden)

    Peter eLewinski

    2015-09-01

    Full Text Available Little is known about people’s accuracy of recognizing neutral faces as neutral. In this paper, I demonstrate the importance of knowing how well people recognize neutral faces. I contrasted human recognition scores of 100 typical, neutral front-up facial images with scores of an arguably objective judge – automated facial coding (AFC software. I hypothesized that the software would outperform humans in recognizing neutral faces because of the inherently objective nature of computer algorithms. Results confirmed this hypothesis. I provided the first-ever evidence that computer software (90% was more accurate in recognizing neutral faces than people were (59%. I posited two theoretical mechanisms, i.e. smile-as-a-baseline and false recognition of emotion, as possible explanations for my findings.

  12. Automated facial coding software outperforms people in recognizing neutral faces as neutral from standardized datasets.

    Science.gov (United States)

    Lewinski, Peter

    2015-01-01

    Little is known about people's accuracy of recognizing neutral faces as neutral. In this paper, I demonstrate the importance of knowing how well people recognize neutral faces. I contrasted human recognition scores of 100 typical, neutral front-up facial images with scores of an arguably objective judge - automated facial coding (AFC) software. I hypothesized that the software would outperform humans in recognizing neutral faces because of the inherently objective nature of computer algorithms. Results confirmed this hypothesis. I provided the first-ever evidence that computer software (90%) was more accurate in recognizing neutral faces than people were (59%). I posited two theoretical mechanisms, i.e., smile-as-a-baseline and false recognition of emotion, as possible explanations for my findings.

  13. The properties of low energy neutral particles in a neutral beam source: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Park, Seung-hoon, E-mail: physh@kaist.ac.k [Department of Physics, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of); Yoo, Suk Jae [National Fusion Research Institute, Daejeon 305-333 (Korea, Republic of); Chang, Choong-Seock [Department of Physics, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of); Courant Institute of Mathematical Sciences, New York University, Mercer Street, New York, NY 10012 (United States)

    2010-09-01

    Application of a hyperthermal neutral beam source is one of the candidate methods of reducing plasma induced damage problems. The neutral beam is generated by vertical collisions between energetic ions and a reflector composed of metal. However, it is difficult to measure the neutral angle and energy distribution experimentally. We simulate the hyperthermal neutral beam (HNB) generation using a molecular dynamics algorithm. In order to obtain a low energy neutral beam, ions with various energies are vertically projected onto the reflector surface. A rough surface structure that has been experimentally measured is used for a realistic simulation. The energy distributions are obtained and the ratio of energy of reflected neutral particles agrees with experimental data.

  14. Increasing the fill factor of inverted P3HT:PCBM solar cells through surface modification of Al-doped ZnO via phosphonic acid-anchored C60 SAMs

    Energy Technology Data Exchange (ETDEWEB)

    Stubhan, Tobias [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Salinas, Michael; Halik, Marcus [Organic Materials and Devices (OMD)-Institute of Polymer Materials, University Erlangen-Nuremberg, Erlangen (Germany); Ebel, Alexander; Hirsch, Andreas [Institute for Organic Chemistry II, Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Krebs, Frederick C. [Risoe National Laboratory for Sustainable Energy, Technical University of Denmark, Roskilde (Denmark); Brabec, Christoph J. [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Bavarian Center for Applied Energy Research (ZAE Bayern), Erlangen (Germany)

    2012-05-15

    The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene-SAMs leads to a reduction of the series resistance, while increasing the parallel resistance. This results in an increased efficiency from 2.9 to 3.3%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Research progress in inorganic-organic hybrid proton exchange membrane based on phosphonic(phosphoric) acid%膦(磷)酸基无机-有机杂化质子交换膜的研究进展

    Institute of Scientific and Technical Information of China (English)

    郭芷含; 沈春晖; 陈成; 孔更金

    2012-01-01

    综述了通过溶胶-凝胶法制备的质子交换膜(PEM),即膦(磷)酸基无机-有机杂化PEM的发展状况.对比分析了掺杂磷酸和键合膦酸无机-有机杂化膜的稳定性以及膦(磷)酸与聚硅氧烷网络结构的连接方式对膜性能的影响.对膦酸基无机.有机杂化膜的发展前景进行了展望.%The development of inorganic-organic hybrid proton exchange membrane(PEM) based on phosphonic(phosphoric) acid was summarized, which were prepared from organosiloxane by sol-gel method. The stability between inorganic-organic hybrid membranes doped phosphoric acid and inorganic-organic hybrid membranes chemically grafted phosphonic acid was compared, then effect of connection ways of phosphonic (phosphoric) acid with the polysiloxane network structure on the membrane performance was discussed. The prospect development of inorganic-organic hybrid membranes based on phosphoric acid was described.

  16. Cofactor-Controlled Chirality of Tropoisomeric Ligand

    NARCIS (Netherlands)

    Théveau, L.; Bellini, R.; Dydio, P.; Szabo, Z.; van der Werf, A.; Sander, R.A.; Reek, J.N.H.; Moberg, C.

    2016-01-01

    A new tropos ligand with an integrated anion receptor receptor site has been prepared. Chiral carboxylate and phosphate anions that bind in the anion receptor unit proved capable of stabilizing chiral conformations of the achiral flexible bidentate biaryl phosphite ligand, as shown by variable

  17. Flexible Ligand Docking Using Evolutionary Algorithms

    DEFF Research Database (Denmark)

    Thomsen, Rene

    2003-01-01

    The docking of ligands to proteins can be formulated as a computational problem where the task is to find the most favorable energetic conformation among the large space of possible protein–ligand complexes. Stochastic search methods such as evolutionary algorithms (EAs) can be used to sample large...

  18. Flexible Ligand Docking Using Differential Evolution

    DEFF Research Database (Denmark)

    Thomsen, René

    2003-01-01

    the most favorable energetic conformation among the large space of possible protein-ligand complexes. Stochastic search methods, such as evolutionary algorithms (EAs), can be used to sample large search spaces effectively and is one of the preferred methods for flexible ligand docking. The differential...

  19. Rhodium olefin complexes of diiminate type ligands

    NARCIS (Netherlands)

    Willems, Sander Theodorus Hermanus

    2003-01-01

    The mono-anionic beta-diiminate ligand (ArNC(CH3)CHC(CH3)NAr) on several previous occasions proved useful in stabilising low coordination numbers for both early and late transition metals. In this thesis the reactivity of the rhodium olefin complexes of one of these beta-diiminate ligands (Ar = 2,6-

  20. Ligand sphere conversions in terminal carbide complexes

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

    2016-01-01

    Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first exam...

  1. Asymmetric catalysis based on tropos ligands.

    Science.gov (United States)

    Aikawa, Kohsuke; Mikami, Koichi

    2012-11-21

    All enantiopure atropisomeric (atropos) ligands essentially require enantiomeric resolution or synthetic transformation from a chiral pool. In sharp contrast, the use of tropos (chirally flexible) ligands, which are highly modular, versatile, and easy to synthesize without enantiomeric resolution, has recently been the topic of much interest in asymmetric catalysis. Racemic catalysts bearing tropos ligands can be applied to asymmetric catalysis through enantiomeric discrimination by the addition of a chiral source, which preferentially transforms one catalyst enantiomer into a highly activated catalyst enantiomer. Additionally, racemic catalysts bearing tropos ligands can also be utilized as atropos enantiopure catalysts obtained via the control of chirality by a chiral source followed by the memory of chirality. In this feature article, our results on the asymmetric catalysis via the combination of various central metals and tropos ligands are summarized.

  2. Autologous HIV-1 neutralizing antibodies: emergence of neutralization-resistant escape virus and subsequent development of escape virus neutralizing antibodies

    DEFF Research Database (Denmark)

    Arendrup, M; Nielsen, C; Hansen, J E

    1992-01-01

    The capacity of consecutive human sera to neutralize sequentially obtained autologous virus isolates was studied. HIV-1 was isolated three times over a 48-164-week period from three individuals immediately after seroconversion and from two individuals in later stages of infection. Development of ...... escape virus may be part of the explanation of the apparent failure of the immune system to control HIV infection.......The capacity of consecutive human sera to neutralize sequentially obtained autologous virus isolates was studied. HIV-1 was isolated three times over a 48-164-week period from three individuals immediately after seroconversion and from two individuals in later stages of infection. Development...

  3. Ligand binding mechanics of maltose binding protein.

    Science.gov (United States)

    Bertz, Morten; Rief, Matthias

    2009-11-13

    In the past decade, single-molecule force spectroscopy has provided new insights into the key interactions stabilizing folded proteins. A few recent studies probing the effects of ligand binding on mechanical protein stability have come to quite different conclusions. While some proteins seem to be stabilized considerably by a bound ligand, others appear to be unaffected. Since force acts as a vector in space, it is conceivable that mechanical stabilization by ligand binding is dependent on the direction of force application. In this study, we vary the direction of the force to investigate the effect of ligand binding on the stability of maltose binding protein (MBP). MBP consists of two lobes connected by a hinge region that move from an open to a closed conformation when the ligand maltose binds. Previous mechanical experiments, where load was applied to the N and C termini, have demonstrated that MBP is built up of four building blocks (unfoldons) that sequentially detach from the folded structure. In this study, we design the pulling direction so that force application moves the two MBP lobes apart along the hinge axis. Mechanical unfolding in this geometry proceeds via an intermediate state whose boundaries coincide with previously reported MBP unfoldons. We find that in contrast to N-C-terminal pulling experiments, the mechanical stability of MBP is increased by ligand binding when load is applied to the two lobes and force breaks the protein-ligand interactions directly. Contour length measurements indicate that MBP is forced into an open conformation before unfolding even if ligand is bound. Using mutagenesis experiments, we demonstrate that the mechanical stabilization effect is due to only a few key interactions of the protein with its ligand. This work illustrates how varying the direction of the applied force allows revealing important details about the ligand binding mechanics of a large protein.

  4. BEAMS3D Neutral Beam Injection Model

    Science.gov (United States)

    McMillan, Matthew; Lazerson, Samuel A.

    2014-09-01

    With the advent of applied 3D fields in Tokamaks and modern high performance stellarators, a need has arisen to address non-axisymmetric effects on neutral beam heating and fueling. We report on the development of a fully 3D neutral beam injection (NBI) model, BEAMS3D, which addresses this need by coupling 3D equilibria to a guiding center code capable of modeling neutral and charged particle trajectories across the separatrix and into the plasma core. Ionization, neutralization, charge-exchange, viscous slowing down, and pitch angle scattering are modeled with the ADAS atomic physics database. Elementary benchmark calculations are presented to verify the collisionless particle orbits, NBI model, frictional drag, and pitch angle scattering effects. A calculation of neutral beam heating in the NCSX device is performed, highlighting the capability of the code to handle 3D magnetic fields. Notice: this manuscript has been authored by Princeton University under Contract Number DE-AC02-09CH11466 with the US Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

  5. Species ages in neutral biodiversity models.

    Science.gov (United States)

    Chisholm, Ryan A; O'Dwyer, James P

    2014-05-01

    Biogeography seeks to understand the mechanisms that drive biodiversity across long temporal and large spatial scales. Theoretical models of biogeography can be tested by comparing their predictions of quantities such as species ages against empirical estimates. It has previously been claimed that the neutral theory of biodiversity and biogeography predicts species ages that are unrealistically long. Any improved theory of biodiversity must rectify this problem, but first it is necessary to quantify the problem precisely. Here we provide analytical expressions for species ages in neutral biodiversity communities. We analyse a spatially implicit metacommunity model and solve for both the zero-sum and non-zero-sum cases. We explain why our new expressions are, in the context of biodiversity, usually more appropriate than those previously imported from neutral molecular evolution. Because of the time symmetry of the spatially implicit neutral model, our expressions also lead directly to formulas for species persistence times and species lifetimes. We use our new expressions to estimate species ages of forest trees under a neutral model and find that they are about an order of magnitude shorter than those predicted previously but still unrealistically long. In light of our results, we discuss different models of biogeography that may solve the problem of species ages.

  6. Color-Neutral Superconducting Quark Matter

    CERN Document Server

    Steiner, A W; Prakash, M; Steiner, Andrew W.; Reddy, Sanjay; Prakash, Madappa

    2002-01-01

    We investigate the consequences of enforcing local color neutrality on the color superconducting phases of quark matter by utilizing the Nambu-Jona-Lasinio model supplemented by diquark and the t'Hooft six-fermion interactions. In neutrino free matter at zero temperature, color neutrality guarantees that the number densities of $u, d, {\\rm and} s$ quarks in the Color-Flavor-Locked (CFL) phase will be equal even with physical current quark masses. Electric charge neutrality follows as a consequence and without the presence of electrons. In contrast, electric charge neutrality in the less symmetric 2-flavor superconducting (2SC) phase with $ud$ pairing requires more electrons than the normal quark phase. The free energy density cost of enforcing color and electric charge neutrality in the CFL phase is lower than that in the 2SC phase, which favors the formation of the CFL phase. With increasing temperature and neutrino content, an unlocking transition occurs from the CFL phase to the 2SC phase with the order of...

  7. Accelerating neutral atoms on a Table top

    Science.gov (United States)

    Krishnamurthy, M.; Rajendran, Rajeev; Madhu, T.; Kpm, Rishad; Narayanan, V.; Krishnakumar, E.

    2013-05-01

    Plasma accelerators driven by super strong laser fields couple unusually large energies to charged particles. Acceleration of neutral atoms from such strongly ionized plasmas have remained elusive. A laser based neutralizer can convert laser accelerated fast ion source to fast neutral atom source. We report a scheme to generate fast Argon atoms (up to 1 MeV) from an optical-field-ionized dense nano-cluster ensemble. Intense, ultrashort pulses ionize each atom in a Ar nanocluster to 8+ and coulomb explode ions to energies up to MeV. We show that in a dense cluster ensemble, the electrons that stream out of the focal volume collisionally excited clusters in the periphery of the focus to high lying Rydberg excited states and form a sheath of electronically excited clusters. Cross sections for reducing ions by charge transfer collisions are orders of magnitude larger with the electronically exited systems. Fast ions that stream through the excited cluster sheath are reduced to neutral atoms with no change in momentum. We show that the scheme can covert ions to neutral atoms with nearly 100% efficiency, transferring 8 electrons per atom in a few mm span of the supersonic jet.

  8. Some metal complexes of three new potentially heptadentate (N4O3) tripodal Schiff base ligands; synthesis, characterizatin and X-ray crystal structure of a novel eight coordinate Gd(III) complex

    Science.gov (United States)

    Golbedaghi, Reza; Moradi, Somaeyh; Salehzadeh, Sadegh; Blackman, Allan G.

    2016-03-01

    The symmetrical and asymmetrical potentially heptadentate (N4O3) tripodal Schiff base ligands (H3L1-H3L3) were synthesized from the condensation reaction of three tripodal tetraamine ligands tpt (trpn), tris (3-aminopropyl) amine; ppe (abap), (2-aminoethyl)bis(3-aminopropyl)amine, and tren, tris(2-aminoethyl)amine, with 5-methoxysalicylaldehyde. Then, the reaction of Ln(III) (Ln = Gd, La and Sm), Al(III), and Fe(III) metal ions with the above ligands was investigated. The resulting compounds were characterized by IR, mass spectrometry and elemental analysis in all cases and NMR spectroscopy in the case of the Schiff base ligands. The X-ray crystal structure of the Gd complex of H3L3 ligand showed that in addition to all donor atoms of the ligand one molecule of H2O is also coordinated to the metal ion and a neutral eight-coordinate complex is formed.

  9. The ligand binding domain controls glucocorticoid receptor dynamics independent of ligand release.

    Science.gov (United States)

    Meijsing, Sebastiaan H; Elbi, Cem; Luecke, Hans F; Hager, Gordon L; Yamamoto, Keith R

    2007-04-01

    Ligand binding to the glucocorticoid receptor (GR) results in receptor binding to glucocorticoid response elements (GREs) and the formation of transcriptional regulatory complexes. Equally important, these complexes are continuously disassembled, with active processes driving GR off GREs. We found that co-chaperone p23-dependent disruption of GR-driven transcription depended on the ligand binding domain (LBD). Next, we examined the importance of the LBD and of ligand dissociation in GR-GRE dissociation in living cells. We showed in fluorescence recovery after photobleaching studies that dissociation of GR from GREs is faster in the absence of the LBD. Furthermore, GR interaction with a target promoter revealed ligand-specific exchange rates. However, using covalently binding ligands, we demonstrated that ligand dissociation is not required for receptor dissociation from GREs. Overall, these studies showed that activities impinging on the LBD regulate GR exchange with GREs but that the dissociation of GR from GREs is independent from ligand dissociation.

  10. Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Diwu, J.; Wang, Shuao; Good, Justin J.; DiStefano, Victoria H.; Albrecht-Schmitt, Thomas E.

    2011-06-06

    The heterobimetallic actinide compound UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O, UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O, and UO₂[C₆H₄(PO₃H)₂](H₂O)·H₂O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C₆H₄(PO₃H)₂]₂·2H₂O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U0.9Pu0.1)O₂[C₆H₄(PO₃H)₂](H₂O)·H₂O, and the Pu(IV) phosphonate, Pu[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Np) and M[C₆H₄(PO₃H)₂]₂·2H₂O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO₂[C₆H₄(PO₃H)₂](H₂O)·3H₂O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Np, Pu) and An[C₆H₄(PO₃H)₂]₂·2H₂O (M = Np, Pu) formulas.

  11. A Measurement of Coherent Neutral Pion Production in Neutrino Neutral Current Interactions in NOMAD experiment

    CERN Document Server

    Kullenberg, C T

    2009-01-01

    We present a study of exclusive neutral pion production in neutrino-nucleus Neutral Current interactions using data from the NOMAD experiment at the CERN SPS. The data correspond to $1.44 \\times 10^6$ muon-neutrino Charged Current interactions in the energy range $2.5 \\leq E_{\

  12. When neutral turns significant: brain dynamics of rapidly formed associations between neutral stimuli and emotional contexts.

    Science.gov (United States)

    Ventura-Bort, Carlos; Löw, Andreas; Wendt, Julia; Dolcos, Florin; Hamm, Alfons O; Weymar, Mathias

    2016-09-01

    The ability to associate neutral stimuli with motivationally relevant outcomes is an important survival strategy. In this study, we used event-related potentials (ERPs) to investigate brain dynamics of associative emotional learning when participants were confronted with multiple heterogeneous information. Participants viewed 144 different objects in the context of 144 different emotional and neutral background scenes. During each trial, neutral objects were shown in isolation and then paired with the background scene. All pairings were presented twice to compare ERPs in response to neutral objects before and after single association. After single pairing, neutral objects previously encoded in the context of emotional scenes evoked a larger P100 over occipital electrodes compared to objects that were previously paired with neutral scenes. Likewise, larger late positive potentials (LPPs) were observed over parieto-occipital electrodes (450-750 ms) for objects previously associated with emotional relative to neutral contexts. The LPP - but not P100 - enhancement was also related to subjective object/context binding. Taken together, our ERP data provide evidence for fast emotional associative learning, as reflected by heightened perceptual and sustained elaborative processing for neutral information previously encountered in emotional contexts. These findings could assist in understanding binding mechanisms in stress and anxiety, as well as in addiction and eating-related disorders. © 2016 Federation of European Neuroscience Societies and John Wiley & Sons Ltd.

  13. Edge rotation from momentum transport by neutrals

    Science.gov (United States)

    Omotani, JT; Newton, SL; Pusztai, I.; Fülöp, T.

    2016-11-01

    Due to their high cross field mobility, neutral atoms can have a strong effect on transport even at the low relative densities found inside the separatrix. We use a charge-exchange dominated model for the neutrals, coupled to neoclassical ions, to calculate momentum transport when it is dominated by the neutrals. We can then calculate self-consistently the radial electric field and predict the intrinsic rotation in an otherwise torque-free plasma. Using a numerical solver for the ion distribution to allow arbitrary collisionality, we investigate the effects of inverse aspect ratio and elongation on plasma rotation. We also calculate the rotation of a trace carbon impurity, to facilitate future comparison to experiments using charge exchange recombination spectroscopy diagnostics.

  14. Broadly Neutralizing Antibodies for HIV Eradication.

    Science.gov (United States)

    Stephenson, Kathryn E; Barouch, Dan H

    2016-02-01

    Passive transfer of antibodies has long been considered a potential treatment modality for infectious diseases, including HIV. Early efforts to use antibodies to suppress HIV replication, however, were largely unsuccessful, as the antibodies that were studied neutralized only a relatively narrow spectrum of viral strains and were not very potent. Recent advances have led to the discovery of a large portfolio of human monoclonal antibodies that are broadly neutralizing across many HIV-1 subtypes and are also substantially more potent. These antibodies target multiple different epitopes on the HIV envelope, thus allowing for the development of antibody combinations. In this review, we discuss the application of broadly neutralizing antibodies (bNAbs) for HIV treatment and HIV eradication strategies. We highlight bNAbs that target key epitopes, such as the CD4 binding site and the V2/V3-glycan-dependent sites, and we discuss several bNAbs that are currently in the clinical development pipeline.

  15. Neutral Delay and a Generalization of Electrodynamics

    CERN Document Server

    De Luca, Jayme

    2010-01-01

    The equations for the electromagnetic two-body problem are neutral-delay equations that for generic initial data have solutions with discontinuous derivatives. If one wants to use these neutral-delay equations with arbitrary initial data, solutions with discontinuous derivatives must be allowed. Surprisingly, this same neutrality is compatible with the recently developed variational method with mixed-type boundaries for the Wheeler-Feynman electrodynamics. We show that two-body electromagnetic orbits with discontinuous velocities are physically necessary by showing that orbits with vanishing far-fields amost everywhere must have some discontinuous velocities on a few points. We generalize the Wheeler-Feynman electrodynamics with the variational method to include all continuous trajectories, allowing piecewise-differentiable weak solutions represented by trajectories with fields defined almost everywhere (but on a set of points of zero measure where velocities jump). Along with this generalization we formulate...

  16. Using Neutral Network in Predicting Corporate Failure

    Directory of Open Access Journals (Sweden)

    Huong G. Nguyen

    2005-01-01

    Full Text Available This study investigates the predictive power of three neutral network models: Multi-layer neural network, probabilistic neural network, and logistic regression model in predicting corporate failure. Basing on the database provided by The Corporate Scorecard Group (CSG, we combine financial ratios which deem to be significant predictors of corporate bankruptcy in many previous empirical studies to build our predictive models and test it against the holdout sample. On comparison of the results, we find that three models are good at predicting probability of corporate failure. Moreover, probabilistic neural network model outperforms the others. Therefore, neutral networks are useful and probabilistic neutral network is a promising tool for the prediction of corporate failure.

  17. Correcting ligands, metabolites, and pathways

    Directory of Open Access Journals (Sweden)

    Vriend Gert

    2006-11-01

    Full Text Available Abstract Background A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases, however, treat chemical structures more as illustrations than as a datafield in its own right. Lack of chemical accuracy impedes progress in the areas mentioned above. We present a database of metabolites called BioMeta that augments the existing pathway databases by explicitly assessing the validity, correctness, and completeness of chemical structure and reaction information. Description The main bulk of the data in BioMeta were obtained from the KEGG Ligand database. We developed a tool for chemical structure validation which assesses the chemical validity and stereochemical completeness of a molecule description. The validation tool was used to examine the compounds in BioMeta, showing that a relatively small number of compounds had an incorrect constitution (connectivity only, not considering stereochemistry and that a considerable number (about one third had incomplete or even incorrect stereochemistry. We made a large effort to correct the errors and to complete the structural descriptions. A total of 1468 structures were corrected and/or completed. We also established the reaction balance of the reactions in BioMeta and corrected 55% of the unbalanced (stoichiometrically incorrect reactions in an automatic procedure. The BioMeta database was implemented in PostgreSQL and provided with a web-based interface. Conclusion We demonstrate that the validation of metabolite structures and reactions is a feasible and worthwhile undertaking, and that the validation results can be used to trigger corrections and improvements to BioMeta, our metabolite database. BioMeta provides some tools for rational drug design, reaction searches, and

  18. Evidence for neutral-current diffractive neutral pion production from hydrogen in neutrino interactions on hydrocarbon

    CERN Document Server

    Wolcott, J; Altinok, O; Bercellie, A; Betancourt, M; Bodek, A; Bravar, A; Budd, H; Cai, T; Carneiro, M F; Chvojka, J; Devan, J; Dytman, S A; Diaz, G A; Eberly, B; Endress, E; Felix, J; Fields, L; Galindo, R; Gallagher, H; Golan, T; Gran, R; Harris, D A; Higuera, A; Hurtado, K; Kiveni, M; Kleykamp, J; Kordosky, M; Le, T; Maher, E; Manly, S; Mann, W A; Marshall, C M; Caicedo, D A Martinez; McFarland, K S; McGivern, C L; McGowan, A M; Messerly, B; Miller, J; Mislivec, A; Morfin, J G; Mousseau, J; Naples, D; Nelson, J K; Norrick, A; Nuruzzaman,; Paolone, V; Park, J; Patrick, C E; Perdue, G N; Rakotondravohitra, L; Ramirez, M A; Ray, H; Ren, L; Rimal, D; Rodrigues, P A; Ruterbories, D; Schellman, H; Schmitz, D W; Salinas, C J Solano; Sanchez, S F; Tagg, N; Tice, B G; Valencia, E; Walton, T; Wospakrik, M; Zhang, D

    2016-01-01

    The MINERvA experiment observes an excess of events containing electromagnetic showers relative to the expectation from Monte Carlo simulations in neutral-current neutrino interactions with mean beam energy of 4.5 GeV on a hydrocarbon target. The excess is characterized and found to be consistent with neutral-current neutral pion production with a broad energy distribution peaking at 7 GeV and a total cross section of 0.26 +- 0.02 (stat) +- 0.08 (sys) x 10^{-39} cm^{2}. The angular distribution, electromagnetic shower energy, and spatial distribution of the energy depositions of the excess are consistent with expectations from neutrino neutral-current diffractive neutral pion production from hydrogen in the hydrocarbon target. These data comprise the first direct experimental observation and constraint for a reaction that poses an important background process in neutrino oscillation experiments searching for muon neutrino to electron neutrino oscillations.

  19. Delay-dependent robust stability for neutral systems with mixed discrete-and-neutral delays

    Institute of Scientific and Technical Information of China (English)

    Yong HE; Min WU; Jinhua SHE

    2004-01-01

    This paper focuses on the problem of delay-dependent robust stability of neutral systems with different discrete-and-neutral delays and time-varying structured uncertainties.Some new criteria are presented,in which some free weighting matrices are used to express the relationships between the terms in the Leibniz-Newton formula.The criteria include the information on the size of both neutral-and-discrete delays.It is shown that the present results also include the results for identical discrete-and-neutral delays as special cases.A numerical example illustrates the improvement of the proposed methods over the previous methods and the influences between the discrete and neutral delays.

  20. Anti-Angiogenic Action of Neutral Endopeptidase

    Science.gov (United States)

    2007-11-01

    kidney , intestine, endometrium, adrenal glands, and lung. This enzyme cleaves peptide bonds on the amino side of hydrophobic amino acids and inactivates...Kintscher U et al. Leptin induces endothelial cell migration through Akt, which is inhibited by PPARgamma-ligands. Hypertension 2002; 40: 748–754

  1. 46 CFR 120.376 - Grounded distribution systems (Neutral grounded).

    Science.gov (United States)

    2010-10-01

    ... ELECTRICAL INSTALLATION Power Sources and Distribution Systems § 120.376 Grounded distribution systems... distribution system having a neutral bus or conductor must have the neutral grounded. (c) The neutral or each... generator is connected to the bus, except the neutral of an emergency power generation system must...

  2. Photoproduction of Neutral Pions off Protons

    CERN Document Server

    Crede, V; Wilson, A; Anisovich, A V; Bacelar, J C S; Bantes, R; Bartholomy, O; Bayadilov, D; Beck, R; Beloglazov, Y A; Castelijns, R; Dutz, H; Elsner, D; Ewald, R; Frommberger, F; Funke, Chr; Gregor, R; Gridnev, A; Gutz, E; Hillert, W; Hoffmeister, P; Jaegle, I; Junkersfeld, J; Kalinowsky, H; Kammer, S; Klein, Frank; Klein, Friedrich; Klempt, E; Kotulla, M; Krusche, B; Loehner, H; Lopatin, I V; Lugert, S; Menze, D; Mertens, T; Messchendorp, J G; Metag, V; Nanova, M; Nikonov, V A; Novinski, D; Novotny, R; Ostrick, M; Pant, L M; van Pee, H; Pfeiffer, M; Roy, A; Sarantsev, A V; Schadmand, S; Schmidt, C; Schmieden, H; Schoch, B; Shende, S; Sokhoyan, V; Suele, A; Sumachev, V V; Szczepanek, T; Thoma, U; Trnka, D; Varma, R; Walther, D; Wendel, Ch

    2011-01-01

    Photoproduction of neutral pions has been studied with the CBELSA/TAPS detector in the reaction $\\gamma p\\to p\\pi^0$ for photon energies between 0.85 and 2.50 GeV. The $\\pi^0$ mesons are observed in their dominant neutral decay mode: $\\pi^0\\to\\gamma\\gamma$. For the first time, the differential cross sections cover the very forward region, $\\theta_{\\rm c.m.}<60^\\circ$. A partial-wave analysis of these data within the Bonn-Gatchina framework observes the high-mass resonances: $G_{17}$(2190), $D_{13}$(2080), and $D_{15}$(2070).

  3. Neutral BSM Higgs searches in ATLAS

    CERN Document Server

    Zhang, Lei; The ATLAS collaboration

    2017-01-01

    This paper summarizes the latest results of the neutral heavy BSM Higgs boson search, mainly based on data collected by the ATLAS experiment at a center-of-mass energy of $\\sqrt{s}=13$ TeV in 2015 and 2016, with an integrated luminosity of 3.2-15.4 ${\\rm fb^{-1}}$. Fermionic, bosonic and di-Higgs final states have been investigated in a mass range from 200 GeV to 3000 GeV. No sign for a new heavy neutral resonance has been found in data so far, and stringent upper limits are reported.

  4. Carbon-neutral fuels and energy carriers

    CERN Document Server

    Muradov, Nazim Z

    2011-01-01

    Concerns over an unstable energy supply and the adverse environmental impact of carbonaceous fuels have triggered considerable efforts worldwide to find carbon-free or low-carbon alternatives to conventional fossil fuels. Carbon-Neutral Fuels and Energy Carriers emphasizes the vital role of carbon-neutral energy sources, transportation fuels, and associated technologies for establishing a sustainable energy future. Each chapter draws on the insight of world-renowned experts in such diverse fields as photochemistry and electrochemistry, solar and nuclear energy, biofuels and synthetic fuels, ca

  5. Photoproduction of neutral pions off protons

    Science.gov (United States)

    Crede, V.; Sparks, N.; Wilson, A.; Anisovich, A. V.; Bacelar, J. C. S.; Bantes, R.; Bartholomy, O.; Bayadilov, D.; Beck, R.; Beloglazov, Y. A.; Castelijns, R.; Dutz, H.; Elsner, D.; Ewald, R.; Frommberger, F.; Funke, Chr.; Gregor, R.; Gridnev, A.; Gutz, E.; Hillert, W.; Hoffmeister, P.; Jaegle, I.; Junkersfeld, J.; Kalinowsky, H.; Kammer, S.; Klein, Frank; Klein, Friedrich; Klempt, E.; Kotulla, M.; Krusche, B.; Löhner, H.; Lopatin, I. V.; Lugert, S.; Menze, D.; Mertens, T.; Messchendorp, J. G.; Metag, V.; Nanova, M.; Nikonov, V. A.; Novinski, D.; Novotny, R.; Ostrick, M.; Pant, L. M.; van Pee, H.; Pfeiffer, M.; Roy, A.; Sarantsev, A. V.; Schadmand, S.; Schmidt, C.; Schmieden, H.; Schoch, B.; Shende, S.; Sokhoyan, V.; Süle, A.; Sumachev, V. V.; Szczepanek, T.; Thoma, U.; Trnka, D.; Varma, R.; Walther, D.; Wendel, Ch.

    2011-11-01

    Photoproduction of neutral pions has been studied with the CBELSA/TAPS detector in the reaction γp→pπ0 for photon energies between 0.85 and 2.50 GeV. The π0 mesons are observed in their dominant neutral decay mode: π0→γγ. For the first time, the differential cross sections cover the very forward region, θc.m.<60∘. A partial-wave analysis of these data within the Bonn-Gatchina framework observes the high-mass resonances G17(2190), D13(2080), and D15(2070).

  6. Direct CP violation in neutral kaon decays

    Indian Academy of Sciences (India)

    Wojciech Wiślicki

    2004-03-01

    The final result of the NA48 experiment is presented and performed at the CERN SPS neutral kaon beams, on the direct CP violation parameter Re$('/)$, as measured from the decay rates of neutral kaons into two pions. The data collected in the years 1997-2001 yield the evidence for the direct CP violation with Re$('/)=(14.7± 2.2)× 10^{-4}$. Description of experimental method and systematics, comparison with the corresponding FNAL result and discussion of some implications for the theory are given.

  7. Multicomponent mixtures for cryoprotection and ligand solubilization

    Directory of Open Access Journals (Sweden)

    Lidia Ciccone

    2015-09-01

    Full Text Available Mixed cryoprotectants have been developed for the solubilization of ligands for crystallization of protein–ligand complexes and for crystal soaking. Low affinity lead compounds with poor solubility are problematic for structural studies. Complete ligand solubilization is required for co-crystallization and crystal soaking experiments to obtain interpretable electron density maps for the ligand. Mixed cryo-preserving compounds are needed prior to X-ray data collection to reduce radiation damage at synchrotron sources. Here we present dual-use mixes that act as cryoprotectants and also promote the aqueous solubility of hydrophobic ligands. Unlike glycerol that increases protein solubility and can cause crystal melting the mixed solutions of cryo-preserving compounds that include precipitants and solubilizers, allow for worry-free crystal preservation while simultaneously solubilizing relatively hydrophobic ligands, typical of ligands obtained in high-throughput screening. The effectiveness of these mixture has been confirmed on a human transthyretin crystals both during crystallization and in flash freezing of crystals.

  8. Coordinate unsaturation with fluorinated ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rack, J.L.; Hurlburt, P.K.; Anderson, O.P.; Strauss, S.H. [Colorado State Univ., Ft. Collins, CO (United States)

    1993-12-31

    The preparation and characterization of Zn(OTeF{sub 5}){sub 2} has resulted in a model compound with which to explore the concept of coordinative unsaturation. The coordination of solvents of varying donicity and dielectric constant to the Zn(II) ions in Zn(OTeF{sub 5}){sub 2} was studied by vapor phase monometry, NMR and IR spectroscopy, conductimetry, and X-Ray crystallography. The structures of [Zn(C{sub 6}H{sub 5}NO{sub 2}){sub 2}(OTeF{sub 5})2]2 and Zn(C{sub 6}H{sub 5}NO{sub 2}){sub 3}(OTEF{sub 5}){sub 2} demonstrate the electronic flexibility of some weakly coordinating solvents in that nitrobenzene can function as either an {eta}{sup 1}O or {eta}{sup 2}O,O`-ligand. The dependence of the number of bound solvent molecules and the degree of OTeF{sub 5}{minus} dissociation on solvent donor number and dielectric constant will be presented.

  9. Distribution of unselectively bound ligands along DNA.

    Science.gov (United States)

    Lando, Dmitri Y; Nechipurenko, Yury D

    2008-10-01

    Unselective and reversible adsorption of ligands on DNA for a model of binding proposed by Zasedatelev, Gursky, and Volkenshtein is considered. In this model, the interaction between neighboring ligands located at the distance of i binding centers is characterized by the statistical weight ai. Each ligand covers L binding centers. For this model, expressions for binding averages are represented in a new simple form. This representation is convenient for the calculation of the fraction of inter-ligand distances of i binding centers fd(i) and the fraction of binding centers included in the distances of i binding centers fbc(i) for various types of interaction between bound ligands. It is shown that, for non-cooperative binding, contact cooperativity and long-range cooperativity, the fraction of the zero inter-ligand distance fd(0) is maximal at any relative concentration of bound ligands (r). Calculations demonstrate that, at low r, fd(0) approximately r.ao, and fd(i) approximately r at 11/r-L, then fd(i) rapidly decreases with i at any r for all types of inter-ligand interaction. At high ligand concentration (r is close to rmax=L(-1)), fd(0) is close to unity and fd(i) rapidly decreases with i for any type of inter-ligand interaction. For strong contact cooperativity, fd(0) is close to unity in a much lager r interval ((0.5-1).rmax), and fd(1) approximately ao(-1) at r approximately 0.5.rmax. In the case of long-range interaction between bound ligands, the dependence fd(i) is more complex and has a maximum at i approximately (1/r-L)1/2 for anti-cooperative binding. fbc(i) is maximal at i approximately 1/r-L for all types of binding except the contact cooperativity. A strong asymmetry in the influence of contact cooperativity and anticooperativity on the ligand distribution along DNA is demonstrated.

  10. Half-sandwich pentamethylcyclopentadienyl group 9 metal complexes of 2-aminopyridyl ligands: Synthesis, spectral and molecular study

    Indian Academy of Sciences (India)

    Mahesh Kalidasan; Scott Forbes; Yurij Mozharivskyj; Mohan Rao Kollipara

    2015-06-01

    Thereaction of [Cp*M(-Cl)Cl]2 (M = Rh, Ir) with 2-aminopyridyl based ligands lead to the formation of mononuclear neutral complexes of general formula [Cp*MCl2(L)] {where L1= 2-aminopyridine, L2= 2-amino-3-picoline, L3= 2-amino-3-nirtopyridine, and L4= 2-amino-3-pyridine carboxyaldehyde}. The complexes have been characterized by FT-IR, UV-Vis, 1H-13C NMR and mass spectroscopic methods. X-ray crystallographic studies of the complexes have shown typical piano-stool geometry around the metal centre in which 2-aminopyridyl ligand acts as an N-monodentate ligand and the amino functionality is not involved in metal coordination. The intra/intermolecular arrangement is due to hydrogen bonding.

  11. Calculation of the Dose of Samarium-153-Ethylene Diamine Tetramethylene Phosphonate (153Sm-EDTMP as a Radiopharmaceutical for Pain Relief of bone Metastasis

    Directory of Open Access Journals (Sweden)

    Fatemeh Razghandi

    2016-04-01

    Full Text Available Introduction One of the important applications of nuclear physics in medicine is the use of radioactive elements as radiopharmaceuticals. Metastatic bone disease is the most common form of malignant bone tumors. Samarium-153-ethylene diamine tetramethylene phosphonate (153Sm-EDTMP as a radiopharmaceutical is used for pain palliation. This radiopharmaceutical usually emits beta particles, which have a high uptake in bone tissues. The purpose of this study was to calculate the radiation dose distribution of 153Sm-EDTMP in bone and other tissues, using MCNPX Monte Carlo code in the particle transport model. Materials and Methods Dose delivery to the bone was simulated by seeking radiopharmaceuticals on the bone surface. The phantom model had a simple cylindrical geometry and included bone, bone marrow, and soft tissue. Results The simulation results showed that a significant amount of radiation dose was delivered to the bone by the use of this radiopharmaceutical. Conclusion Thebone acted as a fine protective shield against rays for the bone marrow. Therefore, the trivial absorbed dose by the bone marrow caused less damage to bone-making cells. Also, the high absorbed dose of the bone could destroy cancer cells and relieve the pain in the bone.

  12. Synergistic effects of expandable graphite and dimethyl methyl phosphonate on the mechanical properties, fire behavior, and thermal stability of a polyisocyanurate-polyurethane foam

    Institute of Scientific and Technical Information of China (English)

    Hu Xiangming; Wang Deming; Wang Shuailing

    2013-01-01

    In this study,a series of flame-retardant polyisocyanurate-polyurethane (PIR-PUR) foams were prepared using various concentrations (0-25% by weight) of expandable graphite (EG) and dimethyl methyl phosphonate (DMMP) (0-7% by weight).The effect of these additives on the properties of the PIR-PUR foams,including physico-mechanical,morphological,flame retardancy,and thermal stability,was studied.Increasing amounts of EG in the PIR-PUR foam caused a significant drop in the compression strength.However,DMMP caused the mechanical properties of PIR-PUR foam to improve compared to foam filled with EG alone.The flame retardancy of PIR-PUR foams containing both EG and DMMP was enhanced significantly compared to EG filled foams.Thermogravimetric analysis (TGA) indicated that EG enhances the thermal stability of PIR-PUR foams but that DMMP decreased it.The morphology of the residual char provided conclusive evidence for the weak thermal stability of foams filled with DMMP.

  13. Insights into the mechanism of action of cidofovir and other acyclic nucleoside phosphonates against polyoma- and papillomaviruses and non-viral induced neoplasia.

    Science.gov (United States)

    Andrei, G; Topalis, D; De Schutter, T; Snoeck, R

    2015-02-01

    Acyclic nucleoside phosphonates (ANPs) are well-known for their antiviral properties, three of them being approved for the treatment of human immunodeficiency virus infection (tenofovir), chronic hepatitis B (tenofovir and adefovir) or human cytomegalovirus retinitis (cidofovir). In addition, cidofovir is mostly used off-label for the treatment of infections caused by several DNA viruses other than cytomegalovirus, including papilloma- and polyomaviruses, which do not encode their own DNA polymerases. There is considerable interest in understanding why cidofovir is effective against these small DNA tumor viruses. Considering that papilloma- and polyomaviruses cause diseases associated either with productive infection (characterized by high production of infectious virus) or transformation (where only a limited number of viral proteins are expressed without synthesis of viral particles), it can be envisaged that cidofovir may act as antiviral and/or antiproliferative agent. The aim of this review is to discuss the advances in recent years in understanding the mode of action of ANPs as antiproliferative agents, given the fact that current data suggest that their use can be extended to the treatment of non-viral related malignancies.

  14. Valuation of surfactant Phosphonates synthesized in the protection of metal surfaces against corrosion of mild steel in 0.5M H2SO4 media

    Directory of Open Access Journals (Sweden)

    R. Ghibate

    2015-12-01

    Full Text Available In this article, we are interesting to investigate the corrosion inhibition of mild steel in sulfuric acid by two surfactants phospohonates already synthesized namely sodium methyldodecylphosphonate (Pho1 and sodium methyl (11-methacryloyloxyundecyl phosphonate (Pho2. The inhibition performances of Pho1 and Pho2 on mild steel corrosion in 0,5M H2SO4 solution were studied using the electrochemical impedance spectroscopy (EIS, weight loss, and Tafel polarization technics. The experimental results suggest that those surfactants are effective corrosion inhibitors and the inhibition efficiency increases with the increase surfactants concentrations. Polarization measurements proved that the inhibitors behave as mixed-type. EIS diagram appears a large capacitive loop at high frequencies (HF followed by a small inductive loop at low frequencies (LF for Pho2, and the addition of this surfactant inhibitor increases the impedance of electrode. The adsorption of each surfactant on steel surface obeys Langmuir adsorption isotherm. The thermodynamic and kinetic parameters were calculated and discussed. Values of inhibition efficiency calculated from weight loss, Tafel polarization curves, and EIS are in good agreement.

  15. Binding modes of phosphonic acid derivatives adsorbed on TiO2 surfaces: Assignments of experimental IR and NMR spectra based on DFT/PBC calculations

    Science.gov (United States)

    Geldof, D.; Tassi, M.; Carleer, R.; Adriaensens, P.; Roevens, A.; Meynen, V.; Blockhuys, F.

    2017-01-01

    A DFT study on the adsorption of a series of phosphonic acids (PAs) on the TiO2 anatase (101) and (001) surfaces was performed. The adsorption energies and geometries of the most stable binding modes were compared to literature data and the effect of the inclusion of dispersion forces in the energy calculations was gauged. As the (101) surface is the most exposed surface of TiO2 anatase, the calculated chemical shifts and vibrational frequencies of PAs adsorbed on this surface were compared to experimental 31P and 17O NMR and IR data in order to assign the two possible binding modes (mono- and bidentate) to peaks and bands in these spectra; due to the corrugated nature of anatase (101) tridentate binding is not possible on this surface. Analysis of the calculated and experimental 31P chemical shifts indicates that both monodentate and bidentate binding modes are present. For the reactive (001) surface, the results of the calculations indicate that both bi- and tridentate binding modes result in stable systems. Due to the particular sensitivity of 17O chemical shifts to hydrogen bonding and solvent effects, the model used is insufficient to assign these spectra at present. Comparison of calculated and experimental IR spectra leads to the conclusion that IR spectroscopy is not suitable for the characterization of the different binding modes of the adsorption complexes.

  16. The Chemical and Physical Properties of Poly(ε-caprolactone) Scaffolds Functionalised with Poly(vinyl phosphonic acid-co-acrylic acid).

    Science.gov (United States)

    Bassi, A K; Gough, J E; Zakikhani, M; Downes, S

    2011-01-01

    There is a clinical need for a synthetic alternative to bone graft substitute (BGS) derived from demineralised bone matrix. We report the electrospinning of Poly(ε-caprolactone) (PCL) to form a 3-dimensional scaffold for use as a synthetic BGS. Additionally, we have used Poly(vinyl phosphonic acid-co-acrylic acid) (PVPA) to improve bone formation. Fibres were formed using a 10% w/v PCL/acetone solution. Infrared spectroscopy confirmed that the electrospinning process had no effect on the functional groups present in the resulting structure. The electrospun scaffolds were coated with PVPA (PCL/PVPA), and characterised. The stability of the PVPA coating after immersion in culture medium was assessed over 21 days. There was rapid release of the coating until day 2, after which the coating became stable. The wettability of the PCL scaffolds improved significantly, from 123.3 ± 10.8° to 43.3 ± 1.2° after functionalisation with PVPA. The compressive strength of the PCL/PVPA scaffolds (72 MPa) was significantly higher to that of the PCL scaffold (14 MPa), and an intermediate between trabecular and cortical bone (7 MPa and 170 MPa, resp.). The study has demonstrated that the PCL/PVPA scaffold has the desired chemical and biomechanical characteristics required for a material designed to be used as a BGS.

  17. Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.

    Science.gov (United States)

    Guo, Rui; Reiner, Eric J; Bhavsar, Satyendra P; Helm, Paul A; Mabury, Scott A; Braekevelt, Eric; Tittlemier, Sheryl A

    2012-11-01

    A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.

  18. A neutralization-reionization and reactivity mass spectrometry study of the generation of neutral hydroxymethylene.

    Science.gov (United States)

    Lin, Yawei; Crestoni, Maria Elisa; Fornarini, Simonetta; Mayer, Paul M

    2011-06-01

    Neutral hydroxymethylene HCOH is an important intermediate in several chemical reactions; however, it is difficult to observe due to its high reactivity. In this work, neutral hydroxymethylene and formaldehyde were generated by charge exchange neutralization of their respective ionic counterparts and then were reionized and detected as positive-ion recovery signals in neutralization-reionization mass spectrometry in a magnetic sector instrument of BEE geometry. The reionized species were characterized by their subsequent collision-induced dissociation mass spectra. The transient hydroxymethylene neutral was observed to isomerize to formaldehyde with an experimental time span exceeding 13.9 µs. The vertical neutralization energy of the HCOH(+•) ion has also been assayed using charge transfer reactions between the fast ions and stationary target gases of differing ionization energy. The measured values match the result of ab initio calculations at the QCISD/6-311 + G(d,p) and CCSD(T)/6-311 + + G(3df,2p) levels of theory. Neutral hydroxymethylene was also produced by proton transfer from CH(2) OH(+) to a strong base such as pyridine, confirmed by appropriate isotopic labeling. There is a kinetic isotope effect (KIE) for H(+) versus D(+) transfer from the C atom of the hydroxymethyl cation of ∼3, consistent with a primary KIE of a nearly thermoneutral reaction.

  19. Spatial calibration of a tokamak neutral beam diagnostic using in situ neutral beam emission

    Energy Technology Data Exchange (ETDEWEB)

    Chrystal, C. [Oak Ridge Associated Universities, Oak Ridge, Tennessee 37831 (United States); Burrell, K. H.; Pace, D. C. [General Atomics, P.O. Box 85608, San Diego, California 92186-5608 (United States); Grierson, B. A. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08543-0451 (United States)

    2015-10-15

    Neutral beam injection is used in tokamaks to heat, apply torque, drive non-inductive current, and diagnose plasmas. Neutral beam diagnostics need accurate spatial calibrations to benefit from the measurement localization provided by the neutral beam. A new technique has been developed that uses in situ measurements of neutral beam emission to determine the spatial location of the beam and the associated diagnostic views. This technique was developed to improve the charge exchange recombination (CER) diagnostic at the DIII-D tokamak and uses measurements of the Doppler shift and Stark splitting of neutral beam emission made by that diagnostic. These measurements contain information about the geometric relation between the diagnostic views and the neutral beams when they are injecting power. This information is combined with standard spatial calibration measurements to create an integrated spatial calibration that provides a more complete description of the neutral beam-CER system. The integrated spatial calibration results are very similar to the standard calibration results and derived quantities from CER measurements are unchanged within their measurement errors. The methods developed to perform the integrated spatial calibration could be useful for tokamaks with limited physical access.

  20. Microbially produced extracellular poly-saccharidic Pu(IV)- binding ligands

    Energy Technology Data Exchange (ETDEWEB)

    Hung, C.C.; Roberts, K.A.; Schwehr, K.A.; Santschi, P.H. [Texas A and M University at Galveston, 5007 Ave U, Galveston, TX 77551 (United States)

    2005-07-01

    Full text of publication follows: The investigation of the Pu-binding properties of ligands for diverse extracellular polysaccharides (EPS) is of relevance for the quantitative understanding of colloidal barriers to radionuclide migration. The EPS isolated for this study were from four different bacteria species: a) two aerobic soil bacteria: Shewanella putrefaciens CN32 and Pseudomonas fluorescens Biovar II; and b) one anaerobic bacterium, Clostridium sp. BC1. EPS from these bacteria were isolated through repeated ethanol precipitations. The neutral monosaccharides in the EPS from Pseudomonas florescens Biovar II that were determined by GC-MS consisted of rhamnose, fucose, ribose, arabinose, xylose, mannose, galactose and glucose. The potentially Pu(IV) binding EPS ligands were mainly composed of carboxylic acids and other minor poly-anionic groups, e.g., sulphates and phosphates. Up to 70 % of total carbohydrates were hydrophilic uronic acids, and total carbohydrates made up 23-31% of organic carbon for P. florescens Biovar II and 9-17% of organic carbon for S. putrefaciens CN32. Besides the neutral and acidic sugars in the EPS, there were also 2-13 % of more hydrophobic proteins among these bacterial EPS. Pu binding to these exo-polymers showed log Kd values of about 5 - 6, with results strongly dependent on procedural details (e.g., removal of colloids in Pu(IV) tracer and reagent solutions). We hypothesize that the relative hydrophobicity of the EPS ligands affects the outcome in ternary sorption studies with colloidal silica. Experiments with varying relative hydrophobicities of EPS will elucidate the different sorption strengths and/or attachment potentials of the Pu-binding ligands to inorganic surfaces. (authors)

  1. Neutrino emissivity under neutral kaon condensation

    CERN Document Server

    Kubis, S

    2006-01-01

    Neutrino emissivity from neutron star matter with neutral kaon condensate is considered. It is shown that a new cooling channel is opened, and what is more, all previously known channels acquire the greater emissivity reaching the level of the direct URCA cycle in normal matter.

  2. CP Violation, Neutral Currents, and Weak Equivalence

    Science.gov (United States)

    Fitch, V. L.

    1972-03-23

    Within the past few months two excellent summaries of the state of our knowledge of the weak interactions have been presented. Correspondingly, we will not attempt a comprehensive review but instead concentrate this discussion on the status of CP violation, the question of the neutral currents, and the weak equivalence principle.

  3. Neutron production by neutral beam sources

    Energy Technology Data Exchange (ETDEWEB)

    Berkner, K.H.; Massoletti, D.J.; McCaslin, J.B.; Pyle, R.V.; Ruby, L.

    1979-11-01

    Neutron yields, from interactions of multiampere 40- to 120-keV deuterium beams with deuterium atoms implanted in copper targets, have been measured in order to provide input data for shielding of neutral-deuterium beam facilities for magnetic fusion experiments.

  4. Development of KSTAR Neutral Beam Heating System

    Energy Technology Data Exchange (ETDEWEB)

    Oh, B. H.; Song, W. S.; Yoon, B. J. (and others)

    2007-10-15

    The prototype components of a neutral beam injection (NBI) system have been developed for the KSTAR, and a capability of the manufactured components has been tested. High power ion source, acceleration power supply, other ion source power supplies, neutralizer, bending magnet for ion beam separation, calorimeter, and cryo-sorption pump have been developed by using the domestic technologies and tested for a neutral beam injection of 8 MW per beamline with a pulse duration of 300 seconds. The developed components have been continuously upgraded to achieve the design requirements. The development technology of high power and long pulse neutral beam injection system has been proved with the achievement of 5.2 MW output for a short pulse length and 1.6 MW output for a pulse length of 300 seconds. Using these development technologies, the domestic NB technology has been stabilized under the development of high power ion source, NB beamline components, high voltage and current power supplies, NB diagnostics, NB system operation and control.

  5. If It's Neutral, It's Not Technology

    Science.gov (United States)

    Strate, Lance

    2012-01-01

    Taking a media ecology perspective, this article argues that technology cannot be neutral, because it is a form of change, and it has an inherent bias based on the properties of its materials and methods. Additionally, the application of a technology is an intrinsic part of the technology itself, as is technique, instructions, software, or…

  6. Linear Sweep Voltammetry of Adsorbed Neutral Red.

    Science.gov (United States)

    1982-05-01

    E. Creager, G. T. Marks, D. A. Aikens and H. H. Richtol Prepared for Publication in Journal of Electroanalytical Chemistry Rensselaer Polytechnic... Electroanalytical Chemistry It. KEY WORDS (Continue oun reverse side It necessary mid Ideneliy by block ntaibor) Neutral Red, cyclic voltammetry, adsorbed dye 20

  7. The LIPSS search for light neutral bosons

    Energy Technology Data Exchange (ETDEWEB)

    Andrei Afanasev; Oliver K. Baker; Kevin Beard; George Biallas; James Boyce; Minarni Minarni; Roopchan Ramdon; Michelle D. Shinn; Penny Slocum

    2009-07-01

    An overview is presented of the LIPSS experimental search for very light neutral bosons using laser light from Jefferson Lab's Free Electron Laser. This facility provides very high power beams of photons over a large optical range, particularly at infrared wavelengths. Data has been collected in several experimental runs during the course of the past three years, most recently in the Fall of 2009.

  8. Intraprostatic injection of neutralized zinc in rats

    Energy Technology Data Exchange (ETDEWEB)

    Fahim, M.S.; Wang, M.; Sutcu, M.F.; Fahim, Z.; Safron, J.A.; Ganjam, V.K. (Univ. of Missouri, Columbia (United States) Xian Medical University (China))

    1991-03-11

    Zinc has been implicated in steroid endocrinology of the prostate gland. The conversion of testosterone to dihydrotestosterone (DHT) by 5{alpha}-reductase enzyme is believed to express androgenic responses in the prostate. To note the effect of neutralized zinc on the prostate, 50 sexually mature rats, weighing 325 {plus minus} 20 grams, were divided into 5 groups as follows: (1) control, (2) sham, (3) castrated, (4) injected intraprostatically with 10 mg. neutralized zinc, and (5) injected intraprostatically with 20 mg. neutralized zinc. Results in the treated groups indicated significant reduction of prostate weights, 12% and 53% and histologically normal prostate; no significant change in weight and histological structure of testes, epididymides, and seminal vesicles; significant reduction in 5{alpha}-reductase activity and total protein and DNA concentrations in prostate tissue; and no significant effect on progeny of treated animals. These results suggest that direct application of neutralized zinc to the prostate offers a new modality for treatment of prostatitis without affecting spermatogenesis and testosterone production.

  9. A storage ring for neutral molecules

    NARCIS (Netherlands)

    Crompvoets, F.M.H.

    2005-01-01

    Time-varying inhomogeneous electric fields can be used to manipulate the motion of neutral molecules in phase-space, i.e., position-momentum space, via their electric dipole moment. A theoretical background is given on the motion of the molecules in phase-space. As the forces exerted on the

  10. Atomic Structure Calculations for Neutral Oxygen

    OpenAIRE

    Norah Alonizan; Rabia Qindeel; Nabil Ben Nessib

    2016-01-01

    Energy levels and oscillator strengths for neutral oxygen have been calculated using the Cowan (CW), SUPERSTRUCTURE (SS), and AUTOSTRUCTURE (AS) atomic structure codes. The results obtained with these atomic codes have been compared with MCHF calculations and experimental values from the National Institute of Standards and Technology (NIST) database.

  11. Absence of neutral alkali atoms in rhodizite

    Science.gov (United States)

    Donnay, G.; Thorpe, A.N.; Senftle, F.E.; Sioda, R.

    1966-01-01

    The formula CsB12Be4Al4O28 has been proposed by others for the mineral rhodizite. Electron-spin-resonance and magnetic susceptibility measurements prove the absence of neutral cesium atoms. An ionic formula CsB11Be4Al4O 26(OH)2is proposed.

  12. Neutrino emissivity under neutral kaon condensation

    OpenAIRE

    Kubis, Sebastian

    2005-01-01

    Neutrino emissivity from neutron star matter with neutral kaon condensate is considered. It is shown that a new cooling channel is opened, and what is more, all previously known channels acquire the greater emissivity reaching the level of the direct URCA cycle in normal matter.

  13. If It's Neutral, It's Not Technology

    Science.gov (United States)

    Strate, Lance

    2012-01-01

    Taking a media ecology perspective, this article argues that technology cannot be neutral, because it is a form of change, and it has an inherent bias based on the properties of its materials and methods. Additionally, the application of a technology is an intrinsic part of the technology itself, as is technique, instructions, software, or…

  14. Deprotonation Induced Ligand Oxidation in a Ni-II Complex of a Redox Noninnocent N-1-(2-Aminophenyl)benzene-1,2-diamine and Its Use in Catalytic Alcohol Oxidation

    NARCIS (Netherlands)

    Sikari, R.; Sinha, S.; Jash, U.; Das, S.; Brandão, P.; de Bruin, B.; Paul, N.D.

    2016-01-01

    Two nickel(II)-complexes, [Ni-II(H3L)(2)] (ClO4)(2) ( [1]-(ClO4)(2)) and [Ni-II(HL)(2)] (2), containing the redox-active tridentate ligand N-1-(2-aminophenyl)benzene-1,2-diamine (H3L) have been synthesized. Complex [1] (ClO4)(2) is octahedral containing two neutral H3L ligands in a facial coordinati

  15. Results on intense beam focusing and neutralization from the neutralized beam experiment

    Energy Technology Data Exchange (ETDEWEB)

    Roy, P.K.; Yu, S.S.; Eylon, S.; Henestroza, E.; Anders, A.; Bieniosek, F.M.; Greenway, W.G.; Logan, B.G.; Waldron, W.L.; Vanecek, D.L.; Welch, D.R.; Rose, D.V.; Davidson, R.C.; Efthimion, P.C.; Gilson, E.P.; Sefkow, A.B.; Sharp, W.M.

    2003-10-31

    We have demonstrated experimental techniques to provide active neutralization for space-charge dominated beams as well as to prevent uncontrolled ion beam neutralization by stray electrons. Neutralization is provided by a localized plasma injected from a cathode arc source. Unwanted secondary electrons produced at the wall by halo particle impact are suppressed using a radial mesh liner that is positively biased inside a beam drift tube. We present measurements of current transmission, beam spot size as a function of axial position, beam energy and plasma source conditions. Detailed comparisons with theory are also presented.

  16. Compact Ion and Neutral Mass Spectrometer with Ion Drifts, Temperatures and Neutral Winds

    Science.gov (United States)

    Paschalidis, Nikolaos

    2016-07-01

    In situ measurements of atmospheric neutral and ion composition and density, temperatures, ion drifts and neutral winds, are in high demand to study the dynamics of the ionosphere-theremosphere-mesosphere system. This paper presents a compact Ion and Neutral Mass Spectrometer (INMS) with impended ion drifts and temperature, and neutral winds capability for in situ measurements of ions and neutrals H, He, N, O, N2, O2. The mass resolution M/dM is approximately 10 at an incoming energy range of 0-20eV. The goal is to resolve ion drifts in the range 0 to 3000m/sec with a resolution better than 50m/sec, and neutral winds in the range of 0 to 1000m/sec with similar resolution. For temperatures the goal is to cover a dynamic range of 0 to 5000K. The INMS is based on front end optics for ions and neutrals, pre acceleration, gated time of flight, top hat ESA, MCP detectors and compact electronics. The instrument is redundant for ions and neutrals with the ion and neutral sensor heads on opposite sides and with full electronics in the middle. The ion front end includes RPA for temperature scanning and neutral front end includes angular modulation and thermionic ionization and ion blocking grids. The electronics include fast electric gating, TOF electronics, TOF binning and C&DH digital electronics. The data package includes 400 mass bins each for ions and neutrals and key housekeeping data for instrument health and calibration. The data sampling can be commanded from 0.1 to 10 sec with 1sec nominal setting. The instrument has significant onboard storage capability and a data compression scheme. The mass spectrometer version of the instrument has been flown on the Exocube mission. The instrument occupied 1.5U volume, weighed only 560 g and required nominal power of 1.6W The ExoCube mission was designed to acquire global knowledge of in-situ densities of [H], [He], [O] and H+, He+, O+ in the upper ionosphere and lower exosphere in combination with incoherent scatter radar and

  17. Automated design of ligands to polypharmacological profiles

    Science.gov (United States)

    Besnard, Jérémy; Ruda, Gian Filippo; Setola, Vincent; Abecassis, Keren; Rodriguiz, Ramona M.; Huang, Xi-Ping; Norval, Suzanne; Sassano, Maria F.; Shin, Antony I.; Webster, Lauren A.; Simeons, Frederick R.C.; Stojanovski, Laste; Prat, Annik; Seidah, Nabil G.; Constam, Daniel B.; Bickerton, G. Richard; Read, Kevin D.; Wetsel, William C.; Gilbert, Ian H.; Roth, Bryan L.; Hopkins, Andrew L.

    2012-01-01

    The clinical efficacy and safety of a drug is determined by its activity profile across multiple proteins in the proteome. However, designing drugs with a specific multi-target profile is both complex and difficult. Therefore methods to rationally design drugs a priori against profiles of multiple proteins would have immense value in drug discovery. We describe a new approach for the automated design of ligands against profiles of multiple drug targets. The method is demonstrated by the evolution of an approved acetylcholinesterase inhibitor drug into brain penetrable ligands with either specific polypharmacology or exquisite selectivity profiles for G-protein coupled receptors. Overall, 800 ligand-target predictions of prospectively designed ligands were tested experimentally, of which 75% were confirmed correct. We also demonstrate target engagement in vivo. The approach can be a useful source of drug leads where multi-target profiles are required to achieve either selectivity over other drug targets or a desired polypharmacology. PMID:23235874

  18. Ligand inducible assembly of a DNA tetrahedron.

    Science.gov (United States)

    Dohno, Chikara; Atsumi, Hiroshi; Nakatani, Kazuhiko

    2011-03-28

    Here we show that a small synthetic ligand can be used as a key building component for DNA nanofabrication. Using naphthyridinecarbamate dimer (NCD) as a molecular glue for DNA hybridization, we demonstrate NCD-triggered formation of a DNA tetrahedron.

  19. Nye ligander for Pt-MOF strukturer

    OpenAIRE

    Jakobsen, Søren

    2006-01-01

    Metalorganic frameworks (MOFs) are a new type of compounds which have been intensely investigated during the last few years. They have been synthesized using a wide variety of metals and ligands constructing a vast number of 1, 2 and 3 dimensional structures, some of which possess zeolite-type physics and chemistry. Our approach is to incorporate platinum metal sites into the structures making them bimetallic and potentially catalytically active. Therefore a number of N-N-type ligands (dii...

  20. SnapShot: GPCR-Ligand Interactions.

    Science.gov (United States)

    Ghosh, Eshan; Nidhi, Kumari; Shukla, Arun K

    2014-12-18

    G-protein-coupled receptors enable cells to recognize numerous external stimuli and to transmit corresponding signals across the plasma membrane to trigger appropriate cellular responses. Crystal structures of a number of these receptors have now been determined in inactive and active conformations bound to chemically and functionally distinct ligands. These crystal structures illustrate overall receptor organization and atomic details of ligand-receptor interactions. Copyright © 2014 Elsevier Inc. All rights reserved.