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Sample records for thiaaza crown macrocycles

  1. Complexes of macrocyclic dibenzo-18-crown-6 polyether with nitrates of some rare earths

    International Nuclear Information System (INIS)

    Gren', A.I.; Zakhariya, N.F.; Vityuk, N.V.; Kalishevich, V.S.

    1984-01-01

    The purpose of the investigation is to obtain and study the structure of complexes of macrocyclic polyether dibenzo-18-crown-6(D-18-C-6) with REE nitrates (Ln, Pr, Nd, Er). Synthesis has been realized by mixing the solutions 2 mol Ln(NO 3 ) 3 and 2 mmol D-18-C-6 into 30-50 ml acetonitrile and boiling during 40-60 minutes. Study on the prepared compounds by means of UV- and IR-spectroscopy proved formation of D-18-C-6 complexes with lanthanide nitrates-Ln(NO 3 ) 3 D-18-C-6. Based on studying IR-spectra a conclusion is made on deformation of D-18-C-6 structure under complexing. Distortion of the ring structure of macrocyclic polyether manifests itself in increase of CH 2 -O-CH 2 bond lengths with simultaneous reduction of four other types of bonds C 6 H 5 -O-CH 2 . Synthesized complexes are stated to have different solubility in acetonitrile which increases in the La 3 ) 3 xD-18-C-6 is noted

  2. Some aspects of the extraction separation of actinides by macrocyclic crown compounds

    International Nuclear Information System (INIS)

    Kumar, Anil; Singh, R.K.; Bajpai, D.D.; Shukla, J.P.

    1994-01-01

    Selective and effective extraction-separation of U(VI) and Pu(IV) from aqueous nitric acid media by several crown ethers have been investigated in detail. The critical study of various parameters namely aqueous phase acidity, reagent concentration, diluent, period of equilibration, aqueous to organic phase ratio, strippant and diverse ions, have established the conditions for their optimum extraction. Influence of the introduction of sulfur into a crown ether ring forming a mixed sulfur-oxygen containing macrohetrocycle for improved extraction of actinides is also studied. The species extracted appear to be of ion-pair type, UO 2 (CE) 2+ .2NO 3- and Pu(CE) 2 4+ .4NO 3- formed with U(VI) and Pu(IV), respectively. The apparent extraction equilibrium constant, log Kex, into toluene by DC18C6 with U(VI) is 0.44 and 4.44 for Pu(IV). Recovery of actinides from loaded macrocycles is easily accomplished using dilute oxalic acid, perchloric acid, sulphuric acid or sodium carbonate as the strippants. The lack of interference from even appreciable amounts of possible fission product contaminants is a notable feature of this separation procedure. (author). 20 refs., 6 figs., 6 tabs

  3. Example of uranium(IV) insertion within a macrocyclic crown ether with coexistence of the metal in two oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Bombieri, G; De Paoli, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Immirzi, A

    1978-01-01

    Reaction of UCl/sub 4/ with 18-crown-6 in tetrahydrofuran yields (UCl/sub 4/)/sub 3/ (18-crown-6)/sub 2/ which on recrystallization in nitromethane, gives a partially oxidized and hydrolyzed product whose structure has been investigated by X-ray diffraction. The compound crystallizes in the orthorhombic system. The cell contains eight UCl/sub 3//sup +/ cations each inserted within a crown molecule and four (UO/sub 2/Cl/sub 3/(OH)(H/sub 2/O))/sup 2 -/anions having a pentagonal bipyramidal structure. Four solvated nitromethane molecules are also present. The compound represents one of the very few examples in which uranium exists in two oxidation states, and the first example in which its insertion within a crown macrocycle has been proved by an X-ray diffraction study.

  4. Macrocyclic Gd(3+) complexes with pendant crown ethers designed for binding zwitterionic neurotransmitters.

    Science.gov (United States)

    Oukhatar, Fatima; Meudal, Hervé; Landon, Céline; Logothetis, Nikos K; Platas-Iglesias, Carlos; Angelovski, Goran; Tóth, Éva

    2015-07-27

    A series of Gd(3+) complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd(3+) chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen-type macrocycle that binds the Ln(3+) ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM(-1)  s(-1) at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by (1) H relaxometric titrations of the Gd(3+) complexes and by luminescence measurements on the Eu(3+) and Tb(3+) analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu(3+) complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non-amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis and Characterization of Macrocyclic Polyether N,N'-Diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6.

    Science.gov (United States)

    Toeri, Julius; Laborie, Marie-Pierre

    2016-01-29

    In this study an efficient and direct production procedure for a macrocyclic polyether N,N'-diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6 from the reaction of catechol and N,N-bis(2-chloroethyl)prop-2-en-1-amine in n-butanol in the presence of a strong base is reported. The synthesis involves a two-step addition of sodium hydroxide to enhance the cyclization process, and at the end of the reaction, the reaction mixture is neutralized and the solvent replaced with water in-situ through distillation to afford a relatively pure precipitate that is easily recrystallized from acetone. The yield of the macrocycle was 36%-45% and could be scaled-up to one-mole quantities. The structure and purity of this compound was verified on the basis of elemental analysis, IR, UV-Vis, ¹H-, (13)C-NMR, 2D-NMR, mass spectroscopy, and thermal analysis. The white crystalline compound has a sharp melting point of 124 °C and a crystallization temperature of 81.4 °C determined by differential scanning calorimetry. Our motivation behind the synthesis of the bibracchial lariat azacrown polyether ligand was to examine its possible applications in ion-selective polymer-supported materials.

  6. Synthesis and Characterization of Macrocyclic Polyether N,N′-Diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6

    Directory of Open Access Journals (Sweden)

    Julius Toeri

    2016-01-01

    Full Text Available In this study an efficient and direct production procedure for a macrocyclic polyether N,N′-diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6 from the reaction of catechol and N,N-bis(2-chloroethylprop-2-en-1-amine in n-butanol in the presence of a strong base is reported. The synthesis involves a two-step addition of sodium hydroxide to enhance the cyclization process, and at the end of the reaction, the reaction mixture is neutralized and the solvent replaced with water in-situ through distillation to afford a relatively pure precipitate that is easily recrystallized from acetone. The yield of the macrocycle was 36%–45% and could be scaled-up to one-mole quantities. The structure and purity of this compound was verified on the basis of elemental analysis, IR, UV-Vis, 1H-, 13C-NMR, 2D-NMR, mass spectroscopy, and thermal analysis. The white crystalline compound has a sharp melting point of 124 °C and a crystallization temperature of 81.4 °C determined by differential scanning calorimetry. Our motivation behind the synthesis of the bibracchial lariat azacrown polyether ligand was to examine its possible applications in ion-selective polymer-supported materials.

  7. Crowns and Crypts

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 6. Crowns and Crypts - A Fascinating Group of Multidentate Macrocyclic Ligands. Debasis Bandyopadhyay. General Article Volume 6 Issue 6 June 2001 pp 71-79. Fulltext. Click here to view fulltext PDF. Permanent link:

  8. Multicomponent Syntheses of Macrocycles

    Science.gov (United States)

    Masson, Géraldine; Neuville, Luc; Bughin, Carine; Fayol, Aude; Zhu, Jieping

    How to access efficiently the macrocyclic structure remained to be a challenging synthetic topic. Although many elegant approaches/reactions have been developed, construction of diverse collection of macrocycles is still elusive. This chapter summarized the recently emerged research area dealing with multicomponent synthesis of macrocycles, with particular emphasis on the approach named "multiple multicomponent reaction using two bifunctional building blocks".

  9. Stability complexes of lanthanide ions with some macrocyclic polyethers

    International Nuclear Information System (INIS)

    Poluehktov, N.S.; Malinka, E.V.; Meshkova, S.B.; Bel'tyukova, S.V.; Danilkovich, M.M.

    1984-01-01

    Stability of lanthanide complexes with macrocyclic polyethers has been studied versus the number of f-electrons, spin- and orbital angular momenta of the Lu 3+ ion ground states. The following compounds were used as macrocyclic complexones: 12-crown-4 (12C4), tert-bulylbenzo-15-crown-5(BB15C5), 18-crown-6 (18C6), ditert-butylbenzo-18-crown-6(DBB18C6), dibenzo-30-crown-10 (DB30C10), cryptand [2, 2, 1] (Cr[2, 2, 1]). It is shoWn that the stability constants of the studied lanthanide complexes can be described rather satisfactorily by an expression suggested earlier that relates their values with the number of 4f-electrons and the S and L quantum numbers of the ground states of the lantharide ions

  10. Macrocyclic fragrance materials

    DEFF Research Database (Denmark)

    Salvito, Daniel; Lapczynski, Aurelia; Sachse-Vasquez, Christen

    2011-01-01

    A screening-level aquatic environmental risk assessment for macrocyclic fragrance materials using a “group approach” is presented using data for 30 macrocyclic fragrance ingredients. In this group approach, conservative estimates of environmental exposure and ecotoxicological effects thresholds....../L and for macrocyclic lactones/lactides is 2.7 μg/L. The results of this screening-level aquatic ecological risk assessment indicate that at their current tonnage, often referred to as volumes of use, macrocyclic fragrance materials in Europe and North America, pose a negligible risk to aquatic biota; with no PEC...... for compounds within two subgroups (15 macrocyclic ketones and 15 macrocyclic lactones/lactides) were used to estimate the aquatic ecological risk potential for these subgroups. It is reasonable to separate these fragrance materials into the two subgroups based on the likely metabolic pathway required...

  11. Influence of structure of crown ethers on their radiation stability

    International Nuclear Information System (INIS)

    Grigor'ev, E.I.; Myasoedova, T.G.; Nesterov, S.V.; Trakhtenberg, L.I.

    1988-01-01

    Primary products of γ-radiolysis of crown ethers with the same size of the macrocyclic ring and different substituents were studied by EPR and mass spectrometry. It was shown that introduction of substituents into the polyether ring increases the radiation stability of crown ethers due to intramolecular transfer of energy from the polyether ring to a substituent

  12. Novel macrocyclic carriers for proton-coupled liquid membrane transport. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Lamb, J.D.; Izatt, R.M.; Bradshaw, J.S.; Shirts, R.B.

    1996-08-24

    The objective of this research program is to elucidate the chemical principles which are responsible for the cation selectivity and permeability of liquid membranes containing macrocyclic carriers. Several new macrocyclic carriers were synthesized during the last three year period. In addition, new, more convenient synthetic routes were achieved for several nitrogen-containing bicyclic and tricyclic macrocycles. The cation binding properties of these macrocycles were investigated by potentiometric titration, calorimetric titration, solvent extraction and NMR techniques. In addition, hydrophobic macrocycles were incorporated into dual hollow fiber and other membrane systems to investigate their membrane performance, especially in the proton-coupled transport mode. A study of the effect of methoxyalkyl macrocycle substituents on metal ion transport was completed. A new calorimeter was constructed which made it possible to study the thermodynamics of macrocycle-cation binding to very high temperatures. Measurements of thermodynamic data for the interaction of crown ethers with alkali and alkaline earth cations were achieved to 473 K. Molecular modeling work was begun for the first time on this project and fundamental principles were identified and developed for the establishment of working models in the future.

  13. On solvent extraction of metals by macrocyclic polyethers

    International Nuclear Information System (INIS)

    Ionov, V.P.

    1984-01-01

    The Ksub(γ) parameter characterizing effective ion charges in ionic associates of metal salts is suggested; these charges parallel with other factors determine the metals extraction by macrocyclic polyethers (crown-ethers). The dependence of metal extraction constant on the Ksub(γ) parameter is discussed. It is shown that the less effective cation charge of alkali metal ionic associates, the more probable its entering the crown-ether cavity. The synergetic crown-ethers extraction is bound as well with Ksub(γ) of metal salts. The differences in the cation extraction constants having the same ionic radius are explained with account of different values of Ksub(γ) parameters of these salts

  14. Activity relationships for aromatic crown ethers

    International Nuclear Information System (INIS)

    Wilson, Mark James

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities from molecular modelling and this rational has been applied to the study of proton ionisable and lariating crown ethers. The incorporation of crown ethers into polyamic acid and polyimide frameworks has also been investigated, where the resulting materials have been found to exhibit unusual cation binding and uptake properties. These results imply that the combination of the crown ethers' macrocycle and adjacent carboxylic acid residues, from the polyamic acids, are conducive to effective cationic binding. NMR measurements, in conjunction with molecular modelling, have been used to explore the geometry changes encountered as the crown ether goes from it's uncomplexed to its complexed state. The energy requirement for these geometry changes has subsequently been used to examine the cation selectivity of these materials. The electronic charge changes associated with the complexation have also been investigated and correlated with the theoretical results. (author)

  15. Third Symposium on Macrocyclic Compounds

    International Nuclear Information System (INIS)

    1979-01-01

    At the Third Symposium on Macrocyclic Compounds there were sessions on facilitated transport, analytical applications, organic synthesis and reactions, phase transfer catalysis, and metal complexation. Abstracts of the individual presentations are included

  16. Fourth symposium on macrocyclic compounds

    International Nuclear Information System (INIS)

    Christensen, J.J.; Izatt, R.M.

    1980-01-01

    Both theoretical and experimental aspects of the properties and behavior of synthetic and naturally occurring macrocyclic compounds are covered in this symposium. This document contains abstracts of the papers

  17. Stability constants for some divalent metal ion/crown ether complexes in methanol determined by polarography and conductometry

    NARCIS (Netherlands)

    Chen, L.; Bos, M.; Grootenhuis, P.D.J.; Christenhusz, A.; Hoogendam, E.; Reinhoudt, David; van der Linden, W.E.

    1987-01-01

    Stability constants in methanol at 25.0°C were evaluated for the complexes of the divalent cations Ca2+, Ni2+, Zn2+, Pb2+, Mg2+, Co2+ and Cu2+ with the macrocyclic polyethers 15-crown-5 (15C5), 18-crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6) and dibenzo-24-crown-8 (DB24C8). The log K values of

  18. Response of a benzoxainone derivative linked to monoaza-15-crown-5 with divalent heavy metals.

    Science.gov (United States)

    Addleman, R S; Bennett, J; Tweedy, S H; Elshani, S; Wai, C M

    1998-08-01

    The response of a monoaza-15-crown-5 with an optically active aminobenzoxazinone moiety to divalent cations was investigated. The crown ether was found to undergo a strong emission shift to the blue when complexed with specific divalent metals that have ionic diameters between 1.9-2.4 A. Consequently the photoactive macrocycle is responsive to Mg(2+), Ca(2+), Ba(2+), Sr(2+), Cd(2+), and particularly responsive to Hg(2+)and Pb(2+). Macrocycle emission spectra are shown to be a function of cation concentration. Alkaline metal cations and smaller transition metals ions such as Ni(2+), Co(2+)and Zn(2+)do not cause significant changes in the macrocycle emission spectra. Emission, absorption, and complex stability constants are determined. Mechanisms of cation selectivity and spectral emission shifts are discussed. Challenges involving immobilization of the macrocycle while preserving its spectral response to cations are explored.

  19. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.

    1991-04-01

    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd 0 chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs

  20. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    are macrocyclic structures which have been modeled after the natural product telomestatin or from porphyrin-based ligands discovered in the late 1990s. These two structural classes of G-quadruplex ligands are reviewed here with special attention to selectivity and structure-activity relationships, and with focus...

  1. The coordination chemistry of macrocyclic ligands II

    International Nuclear Information System (INIS)

    Klimes, J.; Knoechel, A.; Rudolph, G.

    1977-01-01

    Compounds of UO 2 (NO 3 ) 2 .6H 2 0 or Th(NO 3 ) 4 .5H 2 0 with five selected crown ethers were prepared according to the method described in Knoeckel et al., Inorg.Nucl.Chem.Lett.; 11:787 (1975). The products were characterized by chemical analysis, NMR, IR and Raman spectroscopy. The results are analyzed and discussed. It is shown that the NO 3 groups remain free after combination, and the H 2 0 groups form the bonds to the polyether. It is concluded that the polyether molecule is attached to two units of UO 2 (NO 3 ) 2 .2H 2 0 (or Th(NO 3 ) 4 .3H 2 0), one each side of the polyether. This would be contrary to the assumption in previous publications, that the U0 2 2+ and Th 4+ ions were coordinated inside the macrocyclic ligand structure. The present hypothesis, however, agrees with a recently published x-ray structure for the uranium compound. In view of the new proposed structure it is suggested that the compounds should be regarded as adducts rather than complexes. (U.K.)

  2. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    Fux, P.

    1984-06-01

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

  3. Absorption infrared spectra of interaction products of cyclic polyethers 18-crown-6 and dibenzo-18-crown-6 with uranyl dinitrate hexahydrate

    International Nuclear Information System (INIS)

    Chumaevskij, N.A.; Belomestnykh, V.I.; Razgonyaeva, G.A.; Shabel'nik, K.S.; Afanas'eva, E.E.

    1988-01-01

    Using the method of IR spectroscopy it is established that during interaction of uranyl nitrate hexahydrate (UNH) with crown-ethers under investigation macrocycles adhere to UO 2 2+ via hydrogen bonds between water molecules and oxygen of polyethers. Interaction of UNH with the above-mentioned crowns leads to conformational rearrangement of cycles of polyethers and improvement of their symmetry, reflecting in noticeable simplification of IR spectra of interaction products as compared to spectra of initial cyclic polyethers

  4. Ionic complexation of N 2O 4 by 18-crown-6

    Science.gov (United States)

    Ricard, S.; Audet, P.; Savoie, R.

    1988-08-01

    An ionic complex has been obtained from N 2O 4 in the presence of the macrocyclic ether 18-crown-6. This crystalline compound has been shown from its Raman spectrum to have the formula NO +·crown·H(NO 3) 2-, with the nitrosonium ion closely associated with the crown ether rather than with the hydrogen dinitrate accompanying ion. This adduct decomposes readily in moist air to give the known complex (HNO 3·H 2O) 2·crown.

  5. Cocomplexation of urea and UO22+ in a Schiff base macrocycle: a mimic of an enzyme binding site

    International Nuclear Information System (INIS)

    van Staveren, C.J.; Fenton, D.E.; Reinhoudt, D.N.; van Eerden, J.; Harkema, S.

    1987-01-01

    As part of the authors work on the complexation of neutral molecules by macrocyclic ligands, they are particularly interested in the complexation of urea. They have shown that urea can form complexes with (aza-)18-crown but the association constants of these complexes in water are very small (18-crown-6-urea, log K/sub s/ = 0.1). Protonation of urea effects stronger binding especially when the crown ether is sufficiently large to form an encapsulated complex (e.g., the complex benzo-27-crown-9-urea-HClO 4 ). Protonation of the weakly basic urea (pK/sub a/ = 0.1, water, 25 0 C) requires strongly acidic conditions and to avoid this they have introduced a covalently linked carboxylic group in the cavity of the macrocycle. A strong hydrogen bond of urea with 2-carboxyl-1,3-xylyl-30-crown-9 results in an encapsulated complex. The concept of using an electrophilic center to bind urea in the cavity of a crown ether proved to be a more general concept. A metal cation can serve as the electrophile as was shown by the isolation and single-crystal X-ray analysis of the 2,6-pyrido-27-crown-9-urea-LiClO 4 (1:2:1) complex in which one of the urea molecules is encapsulated. In an effort to bind an electrophilic metal ion in the crown ethers irreversibly they have concentrated their work on macrocycles of type 1, since the strong binding of quadridentate (salen type) Schiff bases with soft metal ions is well-known

  6. Dinar-crown banknotes

    OpenAIRE

    Pantelić Svetlana

    2017-01-01

    Dinar-crown banknotes were: ½ dinars (i.e. 2 crowns), 1 dinar (i.e. 4 crowns), 5 dinars (i.e. 20 crowns), 10 dinars (i.e. 40 crowns), 20 dinars (i.e. 80 crowns), 100 dinars (i.e. 400 crowns), and 1000 dinars (i.e. 4000 crowns). The ½- and 1-dinar banknotes are assumed to have been issued in 1919, whereas the other five banknotes, according to one source, were released into circulation on 21.02.1920. Pursuant to the regulations, the replacement of the nostrified crown banknotes by the new crow...

  7. The Synthesis, Structures and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

    International Nuclear Information System (INIS)

    Clearfield, Abraham

    2003-01-01

    OAK-B135 The immobilization of crown ethers tends to limit the leveling effect of solvents making the macrocycles more selective. In addition immobilization has the added advantage of relative ease of recovery of the otherwise soluble crown. We have affixed CH2PO3H2 groups to azacrown ethers. The resultant phosphorylated macrocycles may spontaneously aggregate into crystalline supramolecular linear arrays or contacted with cations produce layered or linear polymers. In the linear polymers the metal and phosphonic acids covalently bond into a central stem with the macrocyclic rings protruding from the stem as leaves on a twig. Two types of layered compounds were obtained with group 4 metals. Monoaza-crown ethers form a bilayer where the M4+ plus phosphonic acid groups build the layer and the rings fill the interlayer space. 1, 10-diazadiphosphonic acids cross-link the metal phosphonate layers forming a three-dimensional array of crown ethers. In order to improve diffusion into these 3-D arrays they are spaced by inclusion of phosphate or phosphate groups. Two series of azamacrocylic crown ethers were prepared containing rings with 20 to 32 atoms. These larger rings can complex two cations per ring. Methylene phosphonic acid groups have been bonded to the aza ring atoms to increase the complexing ability of these ligands. Our approach is to carry out acid-base titrations in the absence and presence of cations to determine the pKa values of the protons, both those bonded to aza groups and those associated with the phosphonic acid groups. From the differences in the titration curves obtained with and without the cations present we obtain the stoichiometry of complex formation and the complex stability constants. Some of the applications we are targeting include phase transfer catalysis, separation of cations and the separation of radioisotopes for diagnostic and cancer therapeutic purposes

  8. Studies of flerovium and element 115 homologs with macrocyclic extractants

    Science.gov (United States)

    Despotopulos, John Dustin

    Study of the chemistry of the heaviest elements, Z ? 104, poses a unique challenge due to their low production cross-sections and short half-lives. Chemistry also must be studied on the one-atom-at-a-time scale, requiring automated, fast, and very efficient chemical schemes. Recent studies of the chemical behavior of copernicium (Cn, element 112) and flerovium (Fl, element 114) together with the discovery of isotopes of these elements with half-lives suitable for chemical studies have spurred a renewed interest in the development of rapid systems designed to study the chemical properties of elements with Z ≥ 114. This dissertation explores both extraction chromatography and solvent extraction as methods for development of a rapid chemical separation scheme for the homologs of flerovium (Pb, Sn, Hg) and element 115 (Bi, Sb), with the goal of developing a chemical scheme that, in the future, can be applied to on-line chemistry of both Fl and element 115. Macrocyclic extractants, specifically crown ethers and their derivatives, were chosen for these studies. Carrier-free radionuclides, used in these studies, of the homologs of Fl and element 115 were obtained by proton activation of high purity metal foils at the Lawrence Livermore National Laboratory (LLNL) Center for Accelerator Mass Spectrometry (CAMS): natIn(p,n)113Sn, natSn(p,n)124Sb, and Au(p,n)197m,gHg. The carrier-free activity was separated from the foils by novel separation schemes based on ion exchange and extraction chromatography techniques. Carrier-free Pb and Bi isotopes were obtained from development of a novel generator based on cation exchange chromatography using the 232U parent to generate 212Pb and 212Bi. Crown ethers show high selectivity for metal ions based on their size compared to the negatively charged cavity of the ether. Extraction by crown ethers occur based on electrostatic ion-dipole interactions between the negatively charged ring atoms (oxygen, sulfur, etc.) and the positively

  9. Selective Extraction of Perrhenate and Pertechnetate by New Macrocyclic Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Paviet-Hartmann, Patricia; Horkley, Jared; Wolfrom, Earle [Idaho State University/Idaho National Laboratory, 1776 Science Center Drive, Idaho Falls, ID 83402 (United States); Pak, Joshua [Idaho State University, 921 S. 8th Avenue, Pocatello, ID 83209 (United States)

    2008-07-01

    The long half-life of technetium-99 and its ability to form an anionic species makes it a major concern when considering long-term disposal of high-level radioactive waste. Furthermore, as its most stable species in the environment, the pertechnetate ion, TcO{sub 4}{sup -} is highly mobile and is considered as a long-term hazard in nuclear waste disposal. There is a need for the development of new extractant systems, such as systems based on crown ethers that may serve to selectively extract and separate this long lived radionuclide from different streams for potential industrial application. In this paper, we are reporting the design and synthesis of new macrocyclic compounds to selectively extract technetium and rhenium from complex mixtures. Preliminary tests performed for the selective extraction of pertechnetate and perrhenate are presented. (authors)

  10. Selective Extraction of Perrhenate and Pertechnetate by New Macrocyclic Compounds

    International Nuclear Information System (INIS)

    Paviet-Hartmann, Patricia; Horkley, Jared; Wolfrom, Earle; Pak, Joshua

    2008-01-01

    The long half-life of technetium-99 and its ability to form an anionic species makes it a major concern when considering long-term disposal of high-level radioactive waste. Furthermore, as its most stable species in the environment, the pertechnetate ion, TcO 4 - is highly mobile and is considered as a long-term hazard in nuclear waste disposal. There is a need for the development of new extractant systems, such as systems based on crown ethers that may serve to selectively extract and separate this long lived radionuclide from different streams for potential industrial application. In this paper, we are reporting the design and synthesis of new macrocyclic compounds to selectively extract technetium and rhenium from complex mixtures. Preliminary tests performed for the selective extraction of pertechnetate and perrhenate are presented. (authors)

  11. Great isotope effects in compounding of sodium isotopes by macrocyclic polyether

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1978-01-01

    Isotope effects appear in the compounding of the two sodium isotopes 24 Na + and 22 Na + with macrocyclic polyethers, whose value was determined for the 13 best known polyethers. A radiometric process was used for determining the different half life periods of the nuclides used. To separate the compound and non-compound types, these were distributed between water and chloroform. The isotope ratio in the chloroform phase was compared with the output isotope ratio and the separation facfor determined from this. When using crown ethers, there was enrichment of 24 Na + by a significant amount (large crown ether) up to 3.1 +- 0.4% for 18 crown 6. The remarkably high results can be correlated by Biegeleisen's theory with other chemical conditions. There is a report on the first results of transferring these conditions to the H + /T + system. (orig.) [de

  12. Comprehensive computational design of ordered peptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Hosseinzadeh, Parisa; Bhardwaj, Gaurav; Mulligan, Vikram K.; Shortridge, Matthew D.; Craven, Timothy W.; Pardo-Avila, Fatima; Rettie, Stephan A.; Kim, David E.; Silva, Daniel A.; Ibrahim, Yehia M.; Webb, Ian K.; Cort, John R.; Adkins, Joshua N.; Varani, Gabriele; Baker, David

    2017-12-14

    Mixed chirality peptide macrocycles such as cyclosporine are among the most potent therapeutics identified to-date, but there is currently no way to systematically search through the structural space spanned by such compounds for new drug candidates. Natural proteins do not provide a useful guide: peptide macrocycles lack regular secondary structures and hydrophobic cores and have different backbone torsional constraints. Hence the development of new peptide macrocycles has been approached by modifying natural products or using library selection methods; the former is limited by the small number of known structures, and the latter by the limited size and diversity accessible through library-based methods. To overcome these limitations, here we enumerate the stable structures that can be adopted by macrocyclic peptides composed of L and D amino acids. We identify more than 200 designs predicted to fold into single stable structures, many times more than the number of currently available unbound peptide macrocycle structures. We synthesize and characterize by NMR twelve 7-10 residue macrocycles, 9 of which have structures very close to the design models in solution. NMR structures of three 11-14 residue bicyclic designs are also very close to the computational models. Our results provide a nearly complete coverage of the rich space of structures possible for short peptide based macrocycles unparalleled for other molecular systems, and vastly increase the available starting scaffolds for both rational drug design and library selection methods.

  13. Possible applications of crown-ethers to metal extraction using liquid membrane technology - a literature survey

    International Nuclear Information System (INIS)

    Dozol, M.

    1990-01-01

    Ether-crowns, discovered in 1967 by J.C. PEDERSEN, exhibit attractive complexive and extractive properties, enhanced in various fields, such as analytical chemistry, chemical synthesis, field of biology, or extractive chemistry. The investigations carried out on these macrocyclic compounds are continually increasing, as show in international literature. Among the focus of interest, the applications to metal extraction are extensively studied with crown compounds present in liquid phase or impregnated on supports (membranes or resins). The goal of this paper is to describe the application of crown-ethers to metal extraction, using liquid membrane processes. 69 refs

  14. New Macrocyclic Diamide from Rauvolfia Yunnanensis Tsiang

    Institute of Scientific and Technical Information of China (English)

    GENG Chang-an; LIU Xi-kui

    2008-01-01

    A new macrocyclic diamide, 22-membered macrocyclic diamide, named cyciodicaprylamide(2), and five known compounds, bis(2-ethylhexyl) phthalate(1), ethyl 3,4,5-trimethoxybenzoate(3), ethyl 3,4,5-trimethoxycinnamate (4), (+)-syringaresinol(5), loliolide(6), were isolated from the roots of Rauvolfia yunnanensis Tsiang. Their structures were elucidated based on NMR, 2D NMR, and MS spectrum, respectively. They were obtained from it for the first time.

  15. Comprehensive computational design of ordered peptide macrocycles

    Science.gov (United States)

    Hosseinzadeh, Parisa; Bhardwaj, Gaurav; Mulligan, Vikram Khipple; Shortridge, Matthew D.; Craven, Timothy W.; Pardo-Avila, Fátima; Rettie, Stephen A.; Kim, David E.; Silva, Daniel-Adriano; Ibrahim, Yehia M.; Webb, Ian K.; Cort, John R.; Adkins, Joshua N.; Varani, Gabriele; Baker, David

    2018-01-01

    Mixed-chirality peptide macrocycles such as cyclosporine are among the most potent therapeutics identified to date, but there is currently no way to systematically search the structural space spanned by such compounds. Natural proteins do not provide a useful guide: Peptide macrocycles lack regular secondary structures and hydrophobic cores, and can contain local structures not accessible with L-amino acids. Here, we enumerate the stable structures that can be adopted by macrocyclic peptides composed of L- and D-amino acids by near-exhaustive backbone sampling followed by sequence design and energy landscape calculations. We identify more than 200 designs predicted to fold into single stable structures, many times more than the number of currently available unbound peptide macrocycle structures. Nuclear magnetic resonance structures of 9 of 12 designed 7- to 10-residue macrocycles, and three 11- to 14-residue bicyclic designs, are close to the computational models. Our results provide a nearly complete coverage of the rich space of structures possible for short peptide macrocycles and vastly increase the available starting scaffolds for both rational drug design and library selection methods. PMID:29242347

  16. Squaraine rotaxanes with boat conformation macrocycles.

    Science.gov (United States)

    Fu, Na; Baumes, Jeffrey M; Arunkumar, Easwaran; Noll, Bruce C; Smith, Bradley D

    2009-09-04

    Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocycles with 1,4-phenylene sidewalls and 2,6-pyridine dicarboxamide bridging units are more likely to adopt boat conformations in the solid state than analogous squaraine rotaxane systems with isophthalamide-containing macrocycles. A truncated squaraine dye, with a secondary amine attached directly to the central C(4)O(2) core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is maintained in solution. Encapsulation as a rotaxane increases the dye's brightness by a factor of 6. The encapsulation process appears to constrain the dye and reduce deformation of the chromophore from planarity. This study shows how mechanical encapsulation as a rotaxane can be used as a rational design parameter to fine-tune the chemical and photochemical properties of squaraine dyes.

  17. Macrocyclic receptors immobilized to monodisperse porous polymer particles by chemical grafting and physical impregnation for strontium capture: A comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yang [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing (China); Du, Yi [Department of Chemical Engineering, Laboratory for Advanced Materials, Tsinghua University, Beijing (China); Lv, Dachao [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing (China); Ye, Gang, E-mail: yegang@tsinghua.edu.cn [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing (China); Wang, Jianchen [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing (China)

    2014-06-01

    Graphical abstract: Macrocyclic receptors grafted to monodisperse porous polymer particles for Sr(II) capture. - Highlights: • Synthesis of novel selective Sr adsorbent grafted with macrocyclic receptors. • New monodisperse porous polymer particles used to promote Sr adsorption. • Comparative study and discussion on adsorption behaviour and mechanism. • A chromatographic process proposed for Sr separation in simulated HLLW. - Abstract: Separation of strontium is of great significance for radioactive waste treatment and environmental remediation after nuclear accidents. In this work, a novel class of adsorbent (Crown-g-MPPPs) was synthesized by chemical grafting a macrocyclic ether receptor to monodisperse porous polymer particles (MPPPs) for strontium adsorption. Meanwhile, a counterpart material (Crown@MPPPs) with the receptor molecules immobilized to the MPPPs substrate by physical impregnation was prepared. To investigate how the immobilization manner and distribution of the receptors influence the adsorption ability, a comparative study on the adsorption behaviour of the two materials towards Sr(II) in HNO{sub 3} media was accomplished. Due to the shorter diffusion path and covalently-bonded structure, Crown-g-MPPPs showed faster adsorption kinetics and better stability for cycle use. While Crown@MPPPs had the advantages of facile synthesis and higher adsorption capacity, owing to the absence of conformational constraint to form complexation with Sr(II). Kinetic functions (Lagergren pseudo-first-order/pseudo-second-order functions) and adsorption isotherm models (Langmuir/Freundlich models) were used to fit the experimental data and examine the adsorption mechanism. On this basis, a chromatographic process was proposed by using Crown@MPPPs for an effective separation of Sr(II) (91%) in simulated high level liquid waste (HLLW)

  18. Phosphorus-containing macrocyclic compounds: synthesis and properties

    International Nuclear Information System (INIS)

    Knyazeva, I R; Burilov, Alexander R; Pudovik, Michael A; Habicher, Wolf D

    2013-01-01

    Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are discussed. The bibliography includes 205 references.

  19. Technetium complexation by macrocyclic compounds

    International Nuclear Information System (INIS)

    Li Fan Yu.

    1983-01-01

    Research in nuclear medicine are directed towards the labelling of biological molecules, however, sup(99m)Tc does not show sufficient affinity for these molecules. The aim of this study was to evaluate the ability of macrocyclic compounds to bind strongly technetium in order to be used as complexation intermediate. The reducing agents used were a stannous complex and sodium dithionite. Cryptates and polyesters are not good complexing agents. They form two complexes: a 2:1 sandwich complex or 3:2 and a 1:1 complex. Cyclams are good complexing agents for technetium their complexations strength was determined by competition with pyrophosphate, gluconate and DTPA. Using the method of ligand exchange, the oxidation state of technetium in the Tc-cyclam complex was IV or V. They are 1:1 cationic complexes, the complex charge is +1. The biodistribution in rats of labelling solutions containing (cyclam 14 ane N 4 ) C 12 H 25 shows a good urinary excretion without intoxication risks [fr

  20. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

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

  1. Dinar-crown banknotes

    Directory of Open Access Journals (Sweden)

    Pantelić Svetlana

    2017-01-01

    Full Text Available Dinar-crown banknotes were: ½ dinars (i.e. 2 crowns, 1 dinar (i.e. 4 crowns, 5 dinars (i.e. 20 crowns, 10 dinars (i.e. 40 crowns, 20 dinars (i.e. 80 crowns, 100 dinars (i.e. 400 crowns, and 1000 dinars (i.e. 4000 crowns. The ½- and 1-dinar banknotes are assumed to have been issued in 1919, whereas the other five banknotes, according to one source, were released into circulation on 21.02.1920. Pursuant to the regulations, the replacement of the nostrified crown banknotes by the new crown- dinar banknotes started on 3 February 1920 in Serbia and Montenegro and on 16 February 1920 in other parts of the country. All seven denominations of the dinar-crown banknotes were being withdrawn from circulation throughout a lengthy period of time from 21 February 1921 until May 1934. The first to be withdrawn were the 20-dinar banknotes, from 1 February to 30 April 1921, then the 5-dinar banknotes, from 20 July to 20 November 1922, and the 10-dinar banknotes, from 10 February to 10 June 1924. The 100-dinar (400-crown and 1000-dinar (4000-crown banknotes remained in circulation the longest. The withdrawal of the 100- and 1000-dinar banknotes started in 1929 and lasted until 25 May 1934. The 1924 rulebook on minting coins of ½, 1 and 2 dinars precisely defines their withdrawal from circulation and replacement by minted coins within one year after the last batch of minted coins gets released into circulation. However, in 1927 the decree of the Minister of Finance prescribed that the remaining paper banknotes be withdrawn from circulation on 30 September 1927 by being replaced by the metal coins of the same denominations.

  2. Rapid synthesis of macrocycles from diol precursors

    DEFF Research Database (Denmark)

    Wingstrand, Magnus; Madsen, Charlotte Marie; Clausen, Mads Hartvig

    2009-01-01

    A method for the formation of synthetic macrocycles with different ring sizes from diols is presented. Reacting a simple diol precursor with electrophilic reagents leads to a cyclic carbonate, sulfite or phosphate in a single step in 25-60% yield. Converting the cyclization precursor to a bis-ele...

  3. Concise Synthesis of Macrocycles by Multicomponent Reactions

    NARCIS (Netherlands)

    Abdelraheem, Eman M. M.; Khaksar, Samad; Dömling, Alexander

    2018-01-01

    A short reaction pathway was devised to synthesize a library of artificial 18-27-membered macrocycles. The five-step reaction sequence involves ring opening of a cyclic anhydride with a diamine, esterification, coupling with an amino acid isocyanide, saponification, and, finally, macro-ring closure

  4. Column chromatographic separation of Y3+ from Sr2+ by polymeric ionizable crown ether resins

    International Nuclear Information System (INIS)

    Wood, D.J.; Elshani, S.; Wai, C.M.; Bartsch, R.A.; Huntley, M.; Hartenstein, S.

    1993-01-01

    Condensation polymers containing subunits of crown ether carboxylic acid monomers are effective stationary phases for the chromatographic separation of Y 3+ and Sr 2+ . The pH range and metal loading capacities for the resins have been determined under equilibrium conditions. The resin can be regenerated for repeated use without losing its separation capability. Altering the molecular structure of the monomer (sym-dibenzo-16-crown-5-oxyacetic acid) by an alkyl substitution on the macrocyclic cavity decreases the loading capacity of the resin

  5. Dicyclohexano-18-crown-6 as a novel carrier in the liquid membrane permeation of actinides

    International Nuclear Information System (INIS)

    Kumar, Anil; Singh, R.K.; Bajpai, D.D.; Shukla, J.P.

    1994-01-01

    The proven extractability and profound selectivity of dicyclohexano-18-crown-6 (DC18C6) has been exploited by selecting this crown ether as the ionophore in liquid membrane transport. Macrocycle-facilitated transport of Pu(IV) and U(VI) against their concentration gradient from aqueous nitric acid solutions across organic bulk liquid membrane (BLM) and thin-sheet supported liquid membrane (SLM) containing DC18C6 as the mobile carrier and toluene as the membrane solvent was investigated. (author). 23 refs., 9 tabs., 7 figs

  6. Macrocyclic complexes of radionuclides in nuclear medicine

    International Nuclear Information System (INIS)

    Majkowska, A.; Bilewicz, A.

    2008-01-01

    The use of radiometal-labeled small complexes and biomolecules as diagnostic and therapeutic agents is a relatively new area of medical research. Radiopharmaceuticals are radiolabeled molecules designed to deliver ionizing radiation doses to specific disease sites. Between the targeting biomolecule and a radionuclide a bifunctional ligand is inserted, one end of which is covalently attached to the targeting molecule either directly or through a linker whereas the other strongly coordinates a metallic radionuclide. Selection of a bifunctional ligand is largely determined by the nature and oxidation state of a metal ion. The metal chelate can significantly affect the tumor uptake and biodistribution of radiopharmaceuticals based on small biomolecules. This is because in many cases the metal chelate contributes greatly to the overall size and lipophilicity of the radiopharmaceutical. Therefore, the design and selection of the ligand is very important for the development of a clinically useful therapeutic agent. The requirement for high thermodynamic and kinetic stability of the metal complex is often achieved through the use of macrocyclic ligands with a functionalized arm for covalent bonding to the biomolecule. In this review synthesis of bifunctional macrocyclic ligands and properties of radionuclide macrocyclic complexes used in nuclear medicine are presented. We describe results in two areas: substituted macrocyclic aza ligands for chelation of hard metal cations, and macrocycles containing sulphur for complexation of soft metal cations. Special attention was paid to stability of the complexes as well as to their lipophilicity, which affect biological properties of the formed radiopharmaceuticals. We also include a forecast of the near-term opportunities that are likely to determine practice in the next few years. (authors)

  7. Spectrophotometric method for determination of bifunctional macrocyclic ligands in macrocyclic ligand-protein conjugates

    International Nuclear Information System (INIS)

    Dadachova, E.; Chappell, L.L.; Brechbiel, M.W.

    1999-01-01

    A simple spectrophotometric assay for determination of bifunctional polyazacarboxylate-macrocyclic ligands of different sizes that are conjugated to proteins has been developed for: 12-membered macrocycle DOTA (2-[4-nitrobenzyl]-1, 4, 7, 10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid) and analogs, the 15-membered PEPA macrocycle (2-[4-nitrobenzyl]-1,4,7,10,13-pentaazacyclopentadecane-N,N',N'',N''',N'''' -pentaacetic acid), and the large 18-membered macrocycle HEHA (1,4,7,10,13,16-hexaazacyclooctadecane-N,N',N'',N''',N''''-hexaacetic acid). The method is based on titration of the blue-colored 1:1 Pb(II)-Arsenazo III (AAIII) complex with the polyazacarboxylate macrocyclic ligand in the concentration range of 0-2.5 μM, wherein color change occurring upon transchelation of the Pb(II) from the AAIII to the polyazamacrocyclic ligand is monitored at 656 nm. The assay is performed at ambient temperature within 20 min without any interfering interaction between the protein and Pb(II)-AA(III) complex. Thus, this method also provides a ligand-to-protein ratio (L/P ratio) that reflects the effective number of ligands per protein molecule available to radiolabeling. The method is not suitable for 14-membered TETA macrocycle (2-[4-nitrobenzyl]-1, 4, 8, 11-tetraazacyclotetradecane N,N',N'',N'''-tetraacetic acid) because of low stability constant of Pb(II)-TETA complex. The method is rapid, simple and may be customized for other polyazacarboxylate macrocyclic ligands

  8. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    International Nuclear Information System (INIS)

    Zakurdaeva, O.A.; Nesterov, S.V.; Moscow State Univ.; Feldman, V.I.

    2013-01-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH 3 (CH 2 ) 6 C circle HOH and interior-type alkyl R 1 C circle HR 2 OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH 2 -C circle H- and acyclic -C circle H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  9. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    Energy Technology Data Exchange (ETDEWEB)

    Zakurdaeva, O.A.; Nesterov, S.V. [Russian Academy of Sciences, Moscow (Russian Federation). Enikolopov Institute of Synthetic Polymer Materials; Moscow State Univ. (Russian Federation). Dept. of Chemistry; Feldman, V.I. [Moscow State Univ. (Russian Federation). Dept. of Chemistry

    2013-03-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH{sub 3}(CH{sub 2}){sub 6}C {sup circle} HOH and interior-type alkyl R{sub 1}C {sup circle} HR{sub 2}OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH{sub 2}-C {sup circle} H- and acyclic -C {sup circle} H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  10. Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

    International Nuclear Information System (INIS)

    Tabushi, I.; Yoshizawa, A.

    1986-01-01

    Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

  11. Biomedical potentials of crown ethers: prospective antitumor agents.

    Science.gov (United States)

    Kralj, Marijeta; Tusek-Bozić, Ljerka; Frkanec, Leo

    2008-10-01

    Crown ethers are of enormous interest and importance in chemistry, biochemistry, materials science, catalysis, separation, transport and encapsulated processes, as well as in the design and synthesis of various synthetic systems with specific properties, diverse capabilities, and programmable functions. Classical crown ethers are macrocyclic polyethers that contain 3-20 oxygen atoms separated from each other by two or more carbon atoms. They are exceptionally versatile in selectively binding a range of metal ions and a variety of organic neutral and ionic species. Crown ethers are currently being studied and used in a variety of applications beyond their traditional place in chemistry. This review presents additional applications and the ever-increasing biomedical potentials of these intriguing compounds, with particular emphasis on the prospects of their relevance as anticancer agents. We believe that further research in this direction should be encouraged, as crown compounds could either induce toxicities that are different from those of conventional antitumor drugs, or complement drugs in current use, thereby providing a valuable adjunct to therapy.

  12. Crown Fire Potential

    Data.gov (United States)

    Earth Data Analysis Center, University of New Mexico — Crown fire potential was modeled using FlamMap, an interagency fire behavior mapping and analysis program that computes potential fire behavior characteristics. The...

  13. Macrocyclic receptors immobilized to monodisperse porous polymer particles by chemical grafting and physical impregnation for strontium capture: a comparative study.

    Science.gov (United States)

    Song, Yang; Du, Yi; Lv, Dachao; Ye, Gang; Wang, Jianchen

    2014-06-15

    Separation of strontium is of great significance for radioactive waste treatment and environmental remediation after nuclear accidents. In this work, a novel class of adsorbent (Crown-g-MPPPs) was synthesized by chemical grafting a macrocyclic ether receptor to monodisperse porous polymer particles (MPPPs) for strontium adsorption. Meanwhile, a counterpart material (Crown@MPPPs) with the receptor molecules immobilized to the MPPPs substrate by physical impregnation was prepared. To investigate how the immobilization manner and distribution of the receptors influence the adsorption ability, a comparative study on the adsorption behaviour of the two materials towards Sr(II) in HNO3 media was accomplished. Due to the shorter diffusion path and covalently-bonded structure, Crown-g-MPPPs showed faster adsorption kinetics and better stability for cycle use. While Crown@MPPPs had the advantages of facile synthesis and higher adsorption capacity, owing to the absence of conformational constraint to form complexation with Sr(II). Kinetic functions (Lagergren pseudo-first-order/pseudo-second-order functions) and adsorption isotherm models (Langmuir/Freundlich models) were used to fit the experimental data and examine the adsorption mechanism. On this basis, a chromatographic process was proposed by using Crown@MPPPs for an effective separation of Sr(II) (91%) in simulated high level liquid waste (HLLW). Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Two-Step Macrocycle Synthesis by Classical Ugi Reaction

    NARCIS (Netherlands)

    Abdelraheem, Eman M M; Khaksar, Samad; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; Shaabani, Shabnam; Dömling, Alexander

    2018-01-01

    The direct nonpeptidic macrocycle synthesis of α-isocyano-ω-amines via the classical Ugi four-component reaction (U-4CR) is introduced. Herein an efficient and flexible two-step procedure to complex macrocycles is reported. In the first step, the reaction between unprotected diamines and

  15. Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants

    Energy Technology Data Exchange (ETDEWEB)

    Despotopulos, John D. [Univ. of Nevada, Las Vegas, NV (United States)

    2015-03-12

    Study of the chemistry of the heaviest elements, Z ≥ 104, poses a unique challenge due to their low production cross-sections and short half-lives. Chemistry also must be studied on the one-atom-at-a-time scale, requiring automated, fast, and very efficient chemical schemes. Recent studies of the chemical behavior of copernicium (Cn, element 112) and flerovium (Fl, element 114) together with the discovery of isotopes of these elements with half-lives suitable for chemical studies have spurred a renewed interest in the development of rapid systems designed to study the chemical properties of elements with Z ≥ 114. This dissertation explores both extraction chromatography and solvent extraction as methods for development of a rapid chemical separation scheme for the homologs of flerovium (Pb, Sn, Hg) and element 115 (Bi, Sb), with the goal of developing a chemical scheme that, in the future, can be applied to on-line chemistry of both Fl and element 115. Carrier-free radionuclides, used in these studies, of the homologs of Fl and element 115 were obtained by proton activation of high-purity metal foils at the Lawrence Livermore National Laboratory (LLNL) Center for Accelerator Mass Spectrometry (CAMS): natIn(p,n)113Sn, natSn(p,n)124Sb, and Au(p,n)197m,gHg. The carrier-free activity was separated from the foils by novel separation schemes based on ion exchange and extraction chromatography techniques. Carrier-free Pb and Bi isotopes were obtained from development of a novel generator based on cation exchange chromatography using the 232U parent to generate 212Pb and 212Bi. Macrocyclic extractants, specifically crown ethers and their derivatives, were chosen for these studies; crown ethers show high selectivity for metal ions. Finally. a potential chemical system for Fl was established based on the Eichrom Pb resin, and insight to an improved system based on thiacrown ethers is

  16. Design, Properties and Recent Application of Macrocycles in Medicinal Chemistry.

    Science.gov (United States)

    Ermert, Philipp

    2017-10-25

    Macrocyclic compounds have recently received increasing attention in drug discovery as these compounds offer the potential to modulate difficult targets and to access novel chemotypes. Approaches towards libraries of macrocyclic compounds based on modular organic synthesis and applications of these technology platforms to find and improve biologically active compounds are introduced in this minireview. Alternatively, lead compounds may be obtained by truncation and modification of macrocyclic natural products. Selected medicinal chemistry programs are discussed, illustrating a macrocyclization approach toward ligands with improved properties. The design of such ligands is often informed by X-ray crystal structures of protein-ligand complexes. Efforts to understand cellular permeability and oral bioavailability of cyclic peptides and non-peptidic macrocycles are summarized.

  17. Synthesis of New Macrocyclic Polyamides as Antimicrobial Agent Candidates

    Directory of Open Access Journals (Sweden)

    Osama I. Abd El-Salam

    2012-12-01

    Full Text Available A series of macrocyclic imides and Schiff-bases have been prepared via the cyclocondensation of pyridine-2,6-dicarbonyl dichloride (1 with L-ornithine methyl ester to give the corresponding macrocyclic bisester 2. Treatment of 2 with hydrazine hydrate gave macrocyclic bisacid hydrazide 3, which was used as starting material. Condensation of bishydrazide 3 with diacid anhydrides or aromatic aldehydes in refluxing acetic acid or ethanol gave the corresponding macrocyclic bisimides 4, 5a,b and macrocyclic bis- hydrazones 6a–j, respectively. The structure assignments of the new compounds were based on chemical and spectroscopic evidence. The antimicrobial screening showed that many of these newly synthesized compounds have good antimicrobial activities, comparable to ampicillin and ketaconazole used as reference drugs.

  18. Isotopic shifts in chemical exchange systems. 1. Large isotope effects in the complexation of Na+ isotopes by macrocyclic polyethers

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1981-01-01

    The complexation of 24 Na + and 22 Na + by 18 of the most widely used macrocyclic polyethers (crown ethers and monocyclic and bicyclic aminopolyethers) has been investigated in view of possible equilibrium isotope shifts. Solvated salts and polyether complexes were distributed differently into two phases and isotope ratios determined in both phases. Chloroform/water systems were shown to be particularly suitable to the investigations allowing favorable distribution for Na + and 13 of the 18 polyethers employed. With crown ethers 24 Na + enrichment varied from nonsignficant values (for large crown ethers) up to 3.1 +- 0.4% (18-crown-6). In the case of bicyclic aminopolyethers, ligands with cages of optimum size to accommodate Na + showed 24 Na + enrichment between O (nonsignificant) (2.2/sub B/2./sub B/) and 5.2 +- 1.8% (2.2.1). In contrast, for 2.2.2. and its derivatives, being too large for Na + , 22 Na + enrichment varying from O (nonsignificant) (2.2.2.p) up to 5.4 +- 0.5% (2.2.2.) has been observed. These values are remarkably high. They are explained by different bonding in solvate structure and polyether complex by using the theoretical approach of Bigeleisen

  19. The crown splash

    Science.gov (United States)

    Deegan, Robert; Brunet, Philippe; Eggers, Jens

    2008-11-01

    The impact of a drop onto a liquid layer and the subsequent splash has important implications for diverse physical processes such as air-sea gas transfer, cooling, and combustion. In the crown splash parameter regime, the splash pattern is highly regular. We focus on this case as a model for the mechanism that leads to secondary droplets, and thus explain the drop size distribution resulting from the splash. We show that the mean number of secondary droplets is determined by the most unstable wavelength of the Rayleigh-Plateau instability. Variations from this mean are governed by the width of the spectrum. Our results for the crown splash will provide the basis for understanding more complicated splashes.

  20. /sup 133/Cs NMR study of Cs/sup +/ ion complexes with dibenzo-21-crown-7 and dibenzo-24-crown-8 in some mixed solvents

    Energy Technology Data Exchange (ETDEWEB)

    Rounaghi, G.; Popov, A.I.

    1986-01-01

    Complexation of the cesium ion with macrocyclic ligands, dibenzo-21-crown-7 and dibenzo-24-crown-8, was studied in binary solvent mixtures of dimethylsulfoxide with acetone, acetonitrile, propylene carbonate, pyridine and hexamethylphosphoramide (HMPA) as well as in pyridine-methanol mixtures. In the first four binary mixtures the complexation constants increased with decreasing amounts of dimethylsulfoxide (DMSO), the trend is reversed in the DMSO-HMPA system. In all of the above cases, the variation of the stability constant with composition was monotonic and showed good correlation with the inherent solvating ability of the neat solvents which form the mixture. In the pyridine-methanol system, however, for both complexes, the log Ksub(f) vs composition plots show several changes in direction. This behavior is probably due to a change in the structure of this binary solvent as the composition of the medium is varied.

  1. 133Cs NMR study of Cs+ ion complexes with dibenzo-21-crown-7 and dibenzo-24-crown-8 in some mixed solvents

    International Nuclear Information System (INIS)

    Rounaghi, G.; Popov, A.I.

    1986-01-01

    Complexation of the cesium ion with macrocyclic ligands, dibenzo-21-crown-7 and dibenzo-24-crown-8, was studied in binary solvent mixtures of dimethylsulfoxide with acetone, acetonitrile, propylene carbonate, pyridine and hexamethylphosphoramide (HMPA) as well as in pyridine-methanol mixtures. In the first four binary mixtures the complexation constants increased with decreasing amounts of dimethylsulfoxide (DMSO), the trend is reversed in the DMSO-HMPA system. In all of the above cases, the variation of the stability constant with composition was monotonic and showed good correlation with the inherent solvating ability of the neat solvents which form the mixture. In the pyridine-methanol system, however, for both complexes, the log Ksub(f) vs composition plots show several changes in direction. This behavior is probably due to a change in the structure of this binary solvent as the composition of the medium is varied. (author)

  2. Synthesis of novel symmetrical macrocycle via oxidative homocoupling of bisalkyne

    Energy Technology Data Exchange (ETDEWEB)

    Kamalulazmy, Nurulain; Hassan, Nurul Izzaty [School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)

    2014-09-03

    A novel symmetrical macrocycle has been synthesised via oxidative homocoupling of bisalkyne, diprop-2-ynyl pyridine-2,6-dicarboxylate mediated by copper (I) iodide (CuI) and 4-dimethylaminopyridine (DMAP). The precursor compound was synthesised from 2,6-pyridine dicarbonyl dichloride and propargyl alcohol in the presence of triethylamine. The reaction mixture was stirred overnight and further purified via column chromatograpy with 76% yield. Single crystal for X-ray study was obtained by recrystallization from acetone. Subsequently, a symmetrical macrocycle was synthesised from oxidative homocoupling of precursor compound in open atmosphere. The crude product was purified by column chromatography to furnish macrocycle compound with 5% yield. Both compounds were characterised by IR, {sup 1}H and {sup 13}C NMR and mass spectral techniques. The unusual conformation of the bisalkyne and twisted conformation of designed macrocycle has influence the percentage yield. This has been studied thoroughly by X-ray crystallography and electronic structure calculations.

  3. Structural basis for precursor protein-directed ribosomal peptide macrocyclization

    Science.gov (United States)

    Li, Kunhua; Condurso, Heather L.; Li, Gengnan; Ding, Yousong; Bruner, Steven D.

    2016-01-01

    Macrocyclization is a common feature of natural product biosynthetic pathways including the diverse family of ribosomal peptides. Microviridins are architecturally complex cyanobacterial ribosomal peptides whose members target proteases with potent reversible inhibition. The product structure is constructed by three macrocyclizations catalyzed sequentially by two members of the ATP-grasp family, a unique strategy for ribosomal peptide macrocyclization. Here, we describe the detailed structural basis for the enzyme-catalyzed macrocyclizations in the microviridin J pathway of Microcystis aeruginosa. The macrocyclases, MdnC and MdnB, interact with a conserved α-helix of the precursor peptide using a novel precursor peptide recognition mechanism. The results provide insight into the unique protein/protein interactions key to the chemistry, suggest an origin of the natural combinatorial synthesis of microviridin peptides and provide a framework for future engineering efforts to generate designed compounds. PMID:27669417

  4. Structural basis for precursor protein-directed ribosomal peptide macrocyclization.

    Science.gov (United States)

    Li, Kunhua; Condurso, Heather L; Li, Gengnan; Ding, Yousong; Bruner, Steven D

    2016-11-01

    Macrocyclization is a common feature of natural product biosynthetic pathways including the diverse family of ribosomal peptides. Microviridins are architecturally complex cyanobacterial ribosomal peptides that target proteases with potent reversible inhibition. The product structure is constructed via three macrocyclizations catalyzed sequentially by two members of the ATP-grasp family, a unique strategy for ribosomal peptide macrocyclization. Here we describe in detail the structural basis for the enzyme-catalyzed macrocyclizations in the microviridin J pathway of Microcystis aeruginosa. The macrocyclases MdnC and MdnB interact with a conserved α-helix of the precursor peptide using a novel precursor-peptide recognition mechanism. The results provide insight into the unique protein-protein interactions that are key to the chemistry, suggest an origin for the natural combinatorial synthesis of microviridin peptides, and provide a framework for future engineering efforts to generate designed compounds.

  5. Macrocyclic 2,7-Anthrylene Oligomers.

    Science.gov (United States)

    Yamamoto, Yuta; Wakamatsu, Kan; Iwanaga, Tetsuo; Sato, Hiroyasu; Toyota, Shinji

    2016-05-06

    A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Structural basis of nonribosomal peptide macrocyclization in fungi.

    Science.gov (United States)

    Zhang, Jinru; Liu, Nicholas; Cacho, Ralph A; Gong, Zhou; Liu, Zhu; Qin, Wenming; Tang, Chun; Tang, Yi; Zhou, Jiahai

    2016-12-01

    Nonribosomal peptide synthetases (NRPSs) in fungi biosynthesize important pharmaceutical compounds, including penicillin, cyclosporine and echinocandin. To understand the fungal strategy of forging the macrocyclic peptide linkage, we determined the crystal structures of the terminal condensation-like (C T ) domain and the holo thiolation (T)-C T complex of Penicillium aethiopicum TqaA. The first, to our knowledge, structural depiction of the terminal module in a fungal NRPS provides a molecular blueprint for generating new macrocyclic peptide natural products.

  7. Sorption of lanthanoids by polymer-supported diaza-18-crown-6

    International Nuclear Information System (INIS)

    Bel'tyukova, S.I.; Malinka, E.V.; Kravchenko, T.B.; Roska, A.S.; Zitsmanis, A.Kh.

    1990-01-01

    Sorption of thenoyltrifluoroacetonates of rare earths on polymeric sorbent (copolymer of styrene-divinylbenzene) containing the functional groups of macrocyclic polyether diazo-18-crown-6 is studied. Sorption capacity of a sorbent and sorption coefficients are calculated. It is shgown that Eu 3+ , Sm 3+ and Gd 3+ are sorbed most of all, and Ce 3+ , Pr 3+ , Yb 3+ , Lu 3+ - worst of all. Luminescence properties of the sorption europium adduct is studied. The Eu detection limit in the sorbent is 0.00005 μg/ml, Sm - 0.01 μg/ml

  8. Canada’s Evolving Crown: From a British Crown to a “Crown of Maples”

    Directory of Open Access Journals (Sweden)

    Romaniuk Scott Nicholas

    2014-12-01

    Full Text Available This article examines how instruments have changed the Crown of Canada from 1867 through to the present, how this change has been effected, and the extent to which the Canadian Crown is distinct from the British Crown. The main part of this article focuses on the manner in which law, politics, and policy (both Canadian and non-Canadian have evolved a British Imperial institution since the process by which the federal Dominion of Canada was formed nearly 150 years ago through to a nation uniquely Canadian as it exists today. The evolution of the Canadian Crown has taken place through approximately fifteen discrete events since the time of Canadian confederation on July 1, 1867. These fifteen events are loosely categorized into three discrete periods: The Imperial Crown (1867-1930, A Shared Crown (1931-1981, and The Canadian Crown (1982-present.

  9. An Unusual Pseudo-Coordination Polymer of Dithia-18-Crown-6 with Heavy Metal

    International Nuclear Information System (INIS)

    Kang, Gyeongchan; Park, Inhyeok; Lee, Shimsung

    2012-01-01

    The assembly reactions of 1,10-dithia-18-crown-6 (L) with mercury(II) and/or cadmium(II) salts provide metallosupramolecules with the unusual arrangement due to the formation of the mercury(II) halides (chloride and iodide) clusters which locate outside the macrocyclic cavity. In the reaction with mercury(II) chloride, we were able to isolate the 1D pseudo-coordination polymer 1 which resembles the ivy leaves. In 1, it is considered that the 1D zigzag array of Hg-Cl-Hg-Cl chain as a leaf-stem and the macrocyclic complexes as leaves. While, from the reaction of mercury(II) iodide and cadmium(II) iodide mixture, the discrete complex 2 with two macrocyclic cadmium(II) complex cation parts and one mercury(II) iodide cluster anion part was isolated. In both cases, each metal center is seven-coordinate, being bound to all the donors of L, with its seventh site being occupied by one halide atom, adopting a distorted monocapped trigonal prism

  10. An Unusual Pseudo-Coordination Polymer of Dithia-18-Crown-6 with Heavy Metal

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Gyeongchan [Yeosu High School, Yeosu (Korea, Republic of); Park, Inhyeok; Lee, Shimsung [Gyeongsang National Univ., Jinju (Korea, Republic of)

    2012-11-15

    The assembly reactions of 1,10-dithia-18-crown-6 (L) with mercury(II) and/or cadmium(II) salts provide metallosupramolecules with the unusual arrangement due to the formation of the mercury(II) halides (chloride and iodide) clusters which locate outside the macrocyclic cavity. In the reaction with mercury(II) chloride, we were able to isolate the 1D pseudo-coordination polymer 1 which resembles the ivy leaves. In 1, it is considered that the 1D zigzag array of Hg-Cl-Hg-Cl chain as a leaf-stem and the macrocyclic complexes as leaves. While, from the reaction of mercury(II) iodide and cadmium(II) iodide mixture, the discrete complex 2 with two macrocyclic cadmium(II) complex cation parts and one mercury(II) iodide cluster anion part was isolated. In both cases, each metal center is seven-coordinate, being bound to all the donors of L, with its seventh site being occupied by one halide atom, adopting a distorted monocapped trigonal prism.

  11. Selective CO2 gas adsorption in the narrow crystalline cavities of flexible peptide metallo-macrocycles.

    Science.gov (United States)

    Miyake, Ryosuke; Kuwata, Chika; Masumoto, Yui

    2015-02-21

    Crystalline peptide Ni(ii)-macrocycles (BF4(-) salt) exhibited moderate CO2 gas adsorption (ca. 6-7 CO2 molecules per macrocycle) into very narrow cavities (narrowest part gas in preference to CH4 and N2 gases.

  12. Biosynthesis of macrocyclic diterpenoids in Euphorbia lathyris L

    DEFF Research Database (Denmark)

    Luo, Dan

    documents the investigation of the biosynthetic pathways of macrocyclic diterpenoids known as Euphorbia factors in Euphorbia lathyris L. (caper spurge). These macrocyclic diterpenoids are the current industrial source of ingenol mebutate, which is approved for the treatment of actinic keratosis...

  13. Separation of 90Y from 90Sr by solvent extraction with ionizable crown ethers

    International Nuclear Information System (INIS)

    Wood, D.J.; Elshani, S.; Du, H.S.; Natale, N.R.; Wai, C.M.

    1993-01-01

    Sym-Dibenzo-16-crown-5-oxyacetic acid and its analogues are selective for the extraction of Y 3+ over Sr 2+ from aqueous solutions into chloroform. The selectivity and the pH range of extraction are influenced by the structure of the ligand. The size of the macrocyclic cavity, the tether length of the lariat, the attachment of alkyl functional groups to the lariat, and the identity of the ionizable group can affect selectivity and extraction efficiency. When the carboxylic acid at the terminal end of the lariat is replaced by a hydroxamic acid, the selectivity for Y 3+ over Sr 2+ is significantly increased. Using these ionizable crown ethers as extractants, 90 Y fractions of greater than 99.9% purity can be obtained in a single solvent extraction step from solutions of 90 Sr. 11 refs., 5 figs., 2 tabs

  14. Biologically Active Macrocyclic Compounds – from Natural Products to Diversity‐Oriented Synthesis

    DEFF Research Database (Denmark)

    Madsen, Charlotte Marie; Clausen, Mads Hartvig

    2011-01-01

    Macrocyclic compounds are attractive targets when searching for molecules with biological activity. The interest in this compound class is increasing, which has led to a variety of methods for tackling the difficult macrocyclization step in their synthesis. This microreview highlights some recent...... developments in the synthesis of macrocycles, with an emphasis on chemistry developed to generate libraries of putative biologically active compounds....

  15. Ready to crown

    LENUS (Irish Health Repository)

    McReynolds, David

    2017-04-01

    When multiple teeth or localised segments of the mouth require crowns, the restorative interventions involved can be psychologically and physically demanding for the operator, patient and dental technician alike.1,2 It is important that all parties involved in restorations of this nature hold a shared understanding of the expected outcome of treatment, with a realistic, common end goal in mind right from the very beginning. Such clarity of thought and communication is key to avoiding biological, mechanical and aesthetic failures in the planning and execution of advanced restorative treatments. Biomechanically stable and aesthetically pleasing provisional restorations are an essential aspect of treatment, which allow teeth to be prepared and provisionalised over multiple appointments within the comfort zone of the operator and patient.3

  16. Derivatized Pentadentate Macrocyclic Ligands and Their Transition Metal Complexes

    Directory of Open Access Journals (Sweden)

    Muhammad S. Khan

    2002-06-01

    Full Text Available The reaction of the pendant hydroxyethyl group in the planar pentadentate macrocyclic ligand,1,11-bis(2’-hydroxyethyl-4,8;12,16;17,21-trinitrilo-1,2,10,11-tetraazacyclohenicosa- 2,4,6,9,12,14,18,20-octaene (L2, derived from the condensation of 2,6-pyridinedialdehyde with 6,6’-bis(2’ hydroxyethylhydrazino -2,2’-bipyridine (L1, has been investigated. Esterification reactions are facile, and the reaction of the hydroxyethyl-substituted macrocycle with thionyl chloride yields a chloroethyl derivative. Metal complexes of the new derivatized macrocyclic ligands L3-6having general formula ML3-6X2.nH2O (M = Mn, Fe, Co, Ni, Cu, Zn are readily prepared.

  17. Design and synthesis of chalcone-based macrocyclic polyethers

    Directory of Open Access Journals (Sweden)

    Subrata Jana

    2015-12-01

    Full Text Available A series of chalcone-based macrocyclic ethers have been synthesized. These macrocyclic ethers contain polyether as well as extended conjugation to the benzene ring to function as fluorescent sensor for cations. The modeling studies show that the chalcone part of the receptors remains partially out of plane from the polyether part and the keto moiety of the receptors always directed outwardly in the receptor itself. This may be changed during the recognition of metal ions. The tendency of the fluorophore, to be out of plane, increases with increasing the ring size.

  18. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand

    International Nuclear Information System (INIS)

    Martinez M, V.; Padilla, J.; Ramirez, F.M.

    1992-04-01

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H 2 TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac) 3 . H 2 0] and trihydrated [Dy(acac) 3 .3 H 2 0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP) 2 ] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP) 3 . 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP) 2- (TFP) 1- ] for the Dy(TFP) 2 as a result of the existence of the free radical (TFP' 1- and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  19. Overdenture dengan Pegangan Telescopic Crown

    Directory of Open Access Journals (Sweden)

    Pambudi Santoso

    2014-06-01

    Full Text Available Kaitan presisi merupakan alat retensi mekanis yang menghubungkan antara satu atau lebih pegangan gigi tiruan, yang bertujuan untuk menambah retensi dan/atau stabilisasi. Kaitan presisi dapat digunakan secara luas pada gigi tiruan cekat, gigi tiruan sebagian lepasan, overdenture, implant untuk retensi overdenture, dan protesa maksilo fasial. Overdenture dengan kaitan presisi dapat membantu dalam pembagian beban kunyah, meminimalkan trauma pada gigi pegangan dan jaringan lunak, meminimalkan resorbsi tulang, dan meningkatkan estetik dan pengucapan suara. Salah satu jenis dari kaitan presisi adalah telescopic crown, terdiri dari 2 macam mahkota, yaitu mahkota primer yang melekat secara permanen pada gigi penyangga, dan mahkota sekunder yang melekat pada gigi tiruan. Tujuan pemaparan kasus ini adalah untuk memberikan informasi tentang rehabilitasi pasien edentulous sebagian rahang atas dengan telescopic crown..  Pasien wanita berusia 45 tahun datang ke klinik prostodonsia RSGM Prof.Soedomo dengan keluhan ingin dibuatkan gigi tiruan. Pasien kehilangan gigi 11 12 15 16 17 21 22 24 25 26 dan 27 yang diindikasikan untuk pembuatan overdenture gigi tiruan sebagian lepasan (GTS kerangka logam dengan pegangan telescopic crown pada gigi 13 dan 14 dengan sistem parallel-sided crown. Tahap-tahap pembuatan telescopic crown yaitu mencetak model study dengan catatan gigit pendahuluan. Perawatan saluran dilakukan pada akar gigi 13, dilanjutkan pemasangan pasak fiber serta rewalling dinding bukal. Gigi 13 dan 14 dilakukan preparasi mahkota penuh, dilanjutkan dengan pencetakan model kerja untuk coping primer dan kerangka logam dengan metode double impression. Coping primer disementasi pada gigi penyangga, dilanjutkan pasang coba coping sekunder beserta kerangka logam. Selanjutnya dilakukan pencatatan gigit, pencetakan model kerja, penyusunan gigi dan pasang coba penyusunan gigi pada pasien. Prosedur dilanjutkan dengan proses di laboratorium, serta insersi pada

  20. Schiff base oligopyrrolic macrocycles as ligands for lanthanides and actinides

    International Nuclear Information System (INIS)

    Sessler, Jonathan L.; Melfi, Patricia J.; Tomat, Elisa; Callaway, Wyeth; Huggins, Michael T.; Gordon, Pamela L.; Webster Keogh, D.; Date, Richard W.; Bruce, Duncan W.; Donnio, Bertrand

    2006-01-01

    The coordination of f-block cations with Schiff base oligopyrrolic macrocycles is discussed. Analysis of the mesophase of a uranyl 2,5-diformylpyrrole-derived expanded porphyrin complex through temperature-dependent X-ray diffraction (XRD) methods has provided evidence for liquid-crystalline properties, and for molecular stacking into columns, arranged in a 2D hexagonal lattice. In separate studies, UV-vis spectral analysis has indicated the formation of three new f-block oligopyrrolic complexes. Addition of neptunyl ([NpO 2 ] 2+ ) or plutonyl ([PuO 2 ] 2+ ) chloride salts to the free base of a dipyrromethane-derived Schiff base macrocycle induces an immediate spectral change, namely the growth of a Q-like band at 630 nm. Such changes in the absorption spectra cause a dramatic color change from pale yellow to blue. It is postulated that oxidation of this macrocycle, stimulated by reduction of the metal center, leads to the observed spectral changes. An immediate visible and spectral change is also observed with the reaction of lutetium silylamide (Lu[N(Si(CH 3 ) 3 ) 2 ] 3 ), with a different, tetrapyrrole-containing Schiff base macrocycle. In this case, the formation of a complex with 1:1 metal-to-ligand binding stoichiometry is further supported by MALDI-TOF mass spectrometry

  1. Characterization and crystal structures of new Schiff base macrocyclic compounds

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Ghoran, S.H.; Pojarová, Michaela; Dušek, Michal

    2015-01-01

    Roč. 56, č. 7 (2015), s. 1410-1414 ISSN 0022-4766 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : synthesis * macrocyclic Schiff base * single crystal structure analysis * spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.536, year: 2015

  2. Kinetics of oxidation of nickel(II) aza macrocycles by ...

    Indian Academy of Sciences (India)

    The kinetics of the oxidation of nickel (II) hexaaza and nickel (II) pentaaza macrocycles by the peroxydisulphate anion, S2O8 2-, were studied in aqueous media. Effect of H on reaction rate was also studied. The rate increases with increase of S2OO8 2- concentration. Rates are almost independent of acid between H 4 ...

  3. On-Surface Synthesis and Characterization of Honeycombene Oligophenylene Macrocycles.

    Science.gov (United States)

    Chen, Min; Shang, Jian; Wang, Yongfeng; Wu, Kai; Kuttner, Julian; Hilt, Gerhard; Hieringer, Wolfgang; Gottfried, J Michael

    2017-01-24

    We report the on-surface formation and characterization of [30]-honeycombene, a cyclotriacontaphenylene, which consists of 30 phenyl rings (C 180 H 120 ) and has a diameter of 4.0 nm. This shape-persistent, conjugated, and unsubstituted hexagonal hydrocarbon macrocycle was obtained by solvent-free synthesis on a silver (111) single-crystal surface, making solubility-enhancing alkyl side groups unnecessary. Side products include strained macrocycles with square, pentagonal, and heptagonal shape. The molecules were characterized by scanning tunneling microscopy and density functional theory (DFT) calculations. On the Ag(111) surface, the macrocycles act as molecular quantum corrals and lead to the confinement of surface-state electrons inside the central cavity. The energy of the confined surface state correlates with the size of the macrocycle and is well described by a particle-in-the-box model. Tunneling spectroscopy suggests conjugation within the planar rings and reveals influences of self-assembly on the electronic structure. While the adsorbed molecules appear to be approximately planar, the free molecules have nonplanar conformation, according to DFT.

  4. A macrocyclic ellagitannin trimer, oenotherin T(1), from Oenothera species.

    Science.gov (United States)

    Taniguchi, Shoko; Imayoshi, Yoko; Yabu-uchi, Ryoko; Ito, Hideyuki; Hatano, Tsutomu; Yoshida, Takashi

    2002-01-01

    Oenotherin T(1) was isolated from leaves of Oenothera tetraptera as a major ellagitannin. Its structure, that of a macrocyclic trimer with a new acyl group, an isodehydrovaloneoyl group, was established. This compound was also produced by callus tissues induced from O. laciniata leaves.

  5. Schiff base oligopyrrolic macrocycles as ligands for lanthanides and actinides

    Energy Technology Data Exchange (ETDEWEB)

    Sessler, Jonathan L. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station A5300, University of Texas at Austin, Austin, TX 78712-0165 (United States)]. E-mail: sessler@mail.utexas.edu; Melfi, Patricia J. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station A5300, University of Texas at Austin, Austin, TX 78712-0165 (United States); Tomat, Elisa [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station A5300, University of Texas at Austin, Austin, TX 78712-0165 (United States); Callaway, Wyeth [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station A5300, University of Texas at Austin, Austin, TX 78712-0165 (United States); Huggins, Michael T. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station A5300, University of Texas at Austin, Austin, TX 78712-0165 (United States); Gordon, Pamela L. [C-Chemistry and NMT-Nuclear Materials Technology Divisions, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Webster Keogh, D. [C-Chemistry and NMT-Nuclear Materials Technology Divisions, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Date, Richard W. [Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD (United Kingdom); Bruce, Duncan W. [Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD (United Kingdom); Department of Chemistry, University of York, Heslington, YORK YO10 5DD (United Kingdom); Donnio, Bertrand [Institut de Physique et Chimie des Materiaux de Strasbourg (IPCMS), Groupe des Materiaux Organiques (GMO), CNRS-ULP - UMR 7504, 23 rue du Loess BP 43, F-67034 Strasbourg Cedex 2 (France)

    2006-07-20

    The coordination of f-block cations with Schiff base oligopyrrolic macrocycles is discussed. Analysis of the mesophase of a uranyl 2,5-diformylpyrrole-derived expanded porphyrin complex through temperature-dependent X-ray diffraction (XRD) methods has provided evidence for liquid-crystalline properties, and for molecular stacking into columns, arranged in a 2D hexagonal lattice. In separate studies, UV-vis spectral analysis has indicated the formation of three new f-block oligopyrrolic complexes. Addition of neptunyl ([NpO{sub 2}]{sup 2+}) or plutonyl ([PuO{sub 2}]{sup 2+}) chloride salts to the free base of a dipyrromethane-derived Schiff base macrocycle induces an immediate spectral change, namely the growth of a Q-like band at 630 nm. Such changes in the absorption spectra cause a dramatic color change from pale yellow to blue. It is postulated that oxidation of this macrocycle, stimulated by reduction of the metal center, leads to the observed spectral changes. An immediate visible and spectral change is also observed with the reaction of lutetium silylamide (Lu[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 3}), with a different, tetrapyrrole-containing Schiff base macrocycle. In this case, the formation of a complex with 1:1 metal-to-ligand binding stoichiometry is further supported by MALDI-TOF mass spectrometry.

  6. Agricultural Crown Land in Saskatchewan

    International Nuclear Information System (INIS)

    Pyle, W.E.

    1998-01-01

    The petroleum industry's interest in provincial crown land in the agricultural area of Saskatchewan has grown over the last two decades. Agricultural land is regulated by the Saskatchewan Department of Agriculture and Food, Lands Branch. Since 1974 surface lease contracts by oil and gas companies have increased from 1,400 to the present 3,700. Resource lands are regulated by Saskatchewan Environment and Resource Management. There are 8.8 million acres of crown agricultural land in Saskatchewan, most of which is held without title. Crown land management is meant to provide a long term management approach to crown lands that balances economic, environmental and social benefits for present and future generations. The oil and gas industry is an important participant in crown land management. Revenues from petroleum and gas surface leasing, and seismic licensing totals more than five million dollars annually. In 1995/96, there were 54 companies establishing new oil and gas leases on crown land in Saskatchewan. This paper provides details of current policies which apply to petroleum and gas leasing and seismic exploration, and environmental guidelines for companies developing well sites, compressor and metering stations, access roads and easements. 3 tabs

  7. Actinide/crown ether chemistry

    International Nuclear Information System (INIS)

    Benning, M.M.

    1988-01-01

    A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

  8. Crown rust control on oats

    International Nuclear Information System (INIS)

    Frey, K.J.; Browning, J.A.; Simons, M.D.

    1976-01-01

    Attempts have been made to test the relative effectiveness of EMS treatment for inducing tolerance to crown rust among oat strains Clintland-60 of different ploidy levels. One strain of diploid and one of tetraploid oats were treated with EMS. These two strains are as susceptible to damage from crown rust as are cultivars of hexaploid oats. Multiline cultivars of oats have been shown to provide adequate protection from economic loss due to crown-rust disease in Iowa. Since 1968, eleven multiline cultivars of oats have been released from the Iowa station for use in commercial production in the midwestern USA. During the past two winter seasons, the effectiveness of multiline oat cultivars against crown-rust disease has been researched in Texas, USA, which has a ''long rust season'' of about four months, not an Iowa ''short rust season''. The protection against crown rust afforded by the multiline cultivars appeared equally good in Texas and Iowa. The seasonal productions of crown-rust spores relative to completely resistant and susceptible checks were nearly identical in both environments. Fifteen new isolines of oats have been developed for use in multiline varieties, with seed supplies sufficiently large for immediate use

  9. An ESR study of radiation-chemical transformation of 4,4?(5?)-di-(tert-butylcyclohexano)-18-crown-6 and its solution in 1-octanol at 77 K

    International Nuclear Information System (INIS)

    Zakurdaeva, O.A.; Nesterov, S.V.; Feldman, V.I.; Moscow State University, Moscow

    2010-01-01

    Paramagnetic products stabilized in both 4,4'(5')-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its solution in 1-octanol upon low temperature (77 K) X-rays irradiation were studied by ESR spectroscopy. Macrocyclic -O-C.H-CH 2 - radicals and acyclic O C(H)-C.H-O- radicals were found as main radiolysis products in neat DtBuCH18C6. Fraction of acyclic radicals resulting from the macrocycle cleavage was about 50%. No radical products resulted from t-Bu and cyclohexyl fragments were observed. It was concluded that the primary events were essentially concerned with ionization of the polyether moiety. Irradiation of frozen DtBuCH18C6 solutions in 1-octanol resulted in formation of radicals both from crown ether and alcohol. (author)

  10. A new spermidine macrocyclic alkaloid isolated from Gymnosporia arenicola leaf.

    Science.gov (United States)

    da Silva, Gustavo; Martinho, Ana; Soengas, Raquel González; Duarte, Ana Paula; Serrano, Rita; Gomes, Elsa Teixeira; Silva, Olga

    2015-10-01

    The isolation and structural elucidation of a macrocyclic alkaloid, characterized by the presence of a 13-membered macrolactam ring containing a spermidine unit N-linked to a benzoyl group is hereby reported. The structure of this previously unknown spermidine alkaloid isolated from Gymnosporia arenicola (Celastraceae) leaves has been elucidated by (1)H and (13)C NMR spectroscopy (including bidimensional analysis) and further characterized by high-resolution mass spectrometry and polarimetry. A route for the biosynthesis of this new bioactive macrocycle is proposed and the cytotoxicity of the compound was evaluated against two ATCC cell lines - one normal-derived (MCF10A) and one cancer-derived cell line (MCF7) - using the MTT assay. The alkaloid revealed to be non-cytotoxic against both cell lines. The IC50 values from the cells were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. A diversity-oriented synthesis strategy enabling the combinatorial-type variation of macrocyclic peptidomimetic scaffolds.

    Science.gov (United States)

    Isidro-Llobet, Albert; Hadje Georgiou, Kathy; Galloway, Warren R J D; Giacomini, Elisa; Hansen, Mette R; Méndez-Abt, Gabriela; Tan, Yaw Sing; Carro, Laura; Sore, Hannah F; Spring, David R

    2015-04-21

    Macrocyclic peptidomimetics are associated with a broad range of biological activities. However, despite such potentially valuable properties, the macrocyclic peptidomimetic structural class is generally considered as being poorly explored within drug discovery. This has been attributed to the lack of general methods for producing collections of macrocyclic peptidomimetics with high levels of structural, and thus shape, diversity. In particular, there is a lack of scaffold diversity in current macrocyclic peptidomimetic libraries; indeed, the efficient construction of diverse molecular scaffolds presents a formidable general challenge to the synthetic chemist. Herein we describe a new, advanced strategy for the diversity-oriented synthesis (DOS) of macrocyclic peptidomimetics that enables the combinatorial variation of molecular scaffolds (core macrocyclic ring architectures). The generality and robustness of this DOS strategy is demonstrated by the step-efficient synthesis of a structurally diverse library of over 200 macrocyclic peptidomimetic compounds, each based around a distinct molecular scaffold and isolated in milligram quantities, from readily available building-blocks. To the best of our knowledge this represents an unprecedented level of scaffold diversity in a synthetically derived library of macrocyclic peptidomimetics. Cheminformatic analysis indicated that the library compounds access regions of chemical space that are distinct from those addressed by top-selling brand-name drugs and macrocyclic natural products, illustrating the value of our DOS approach to sample regions of chemical space underexploited in current drug discovery efforts. An analysis of three-dimensional molecular shapes illustrated that the DOS library has a relatively high level of shape diversity.

  12. Accurate and Reliable Prediction of the Binding Affinities of Macrocycles to Their Protein Targets.

    Science.gov (United States)

    Yu, Haoyu S; Deng, Yuqing; Wu, Yujie; Sindhikara, Dan; Rask, Amy R; Kimura, Takayuki; Abel, Robert; Wang, Lingle

    2017-12-12

    Macrocycles have been emerging as a very important drug class in the past few decades largely due to their expanded chemical diversity benefiting from advances in synthetic methods. Macrocyclization has been recognized as an effective way to restrict the conformational space of acyclic small molecule inhibitors with the hope of improving potency, selectivity, and metabolic stability. Because of their relatively larger size as compared to typical small molecule drugs and the complexity of the structures, efficient sampling of the accessible macrocycle conformational space and accurate prediction of their binding affinities to their target protein receptors poses a great challenge of central importance in computational macrocycle drug design. In this article, we present a novel method for relative binding free energy calculations between macrocycles with different ring sizes and between the macrocycles and their corresponding acyclic counterparts. We have applied the method to seven pharmaceutically interesting data sets taken from recent drug discovery projects including 33 macrocyclic ligands covering a diverse chemical space. The predicted binding free energies are in good agreement with experimental data with an overall root-mean-square error (RMSE) of 0.94 kcal/mol. This is to our knowledge the first time where the free energy of the macrocyclization of linear molecules has been directly calculated with rigorous physics-based free energy calculation methods, and we anticipate the outstanding accuracy demonstrated here across a broad range of target classes may have significant implications for macrocycle drug discovery.

  13. Macrocyclic ligands for uranium complexation: Progress report, August 15, 1987-present

    International Nuclear Information System (INIS)

    Potts, K.T.

    1988-03-01

    The synthesis of several macrocyclic ligands, designed by a computer modeling approach for the complexation of the uranyl ion, has now been completed and their structures established. Preliminary indicate that these macrocycles successfully complex the uranyl ion. Other synthetic efforts have led to a variety of intermediates suitable for final ring closure to the desired macrocycles, providing appreciable potential for variation of the macrocyclic peripheral atoms. A 1:1-uranyl ion complex of one of these precursor products has been shown to undergo a DMSO-induced rearrangement to a 2:1 uranyl ion to ligand complex, both structures having been established by single crystal x-ray data. 10 refs

  14. Searching for a path towards a helicene-based macrocycle

    Czech Academy of Sciences Publication Activity Database

    Houska, Václav; Stará, Irena G.; Starý, Ivo

    2017-01-01

    Roč. 15, č. 1 (2017), s. 9-10 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /17./. 30.05.2017-01.06.2017, Milovy] R&D Projects: GA ČR(CZ) GA16-08294S Institutional support: RVO:61388963 Keywords : helicenes * macrocycles Subject RIV: CC - Organic Chemistry

  15. Synthesis and study of lipophilic crown ethers and thia-ligands. Application to nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Guyon, Vincent

    1992-01-01

    In the field of metal extraction from the solutions of nuclear fuel reprocessing, new specific complexing agents that are more efficient than tributyl phosphate must possess a high lipophilic character. The use of lipophilic crown ethers and thia-ligands has eliminated the problem related to their loss in the aqueous media. Moreover, it has made their complexes more soluble in organic solvents. The increase of lipophilic character of monocyclic polyethers has been realized with the addition of an alkyl chain and the development of a new process has made possible the separation of cis-syn-cis and cis-anti-cis isomers of dicyclohexano 18 crown 6 on an industrial scale. The creation of a rapid NMR method of analysis has permitted to study the extracting capacity of those crown ethers in relation to monovalent and divalent cations in nitric acid media and also to demonstrate the influence brought by different substituents. Some new lipophilic thia-ligands (macrocycles and podands) have also been prepared and the study of palladium extraction in nitric acid media by these compounds has led to a better understanding of the relation between the structure and the extracting capacity. Of easy access, some podands have an extracting selectivity and an extracting kinetic for this metal which are highly superior than those of dialkyl sulphides actually employed in the industry. This makes their use possible in the nuclear area. (author) [fr

  16. Wave Forces on Crown Walls

    DEFF Research Database (Denmark)

    Pedersen, Jan; Burcharth, H. F.

    1993-01-01

    This paper presents some of the results from a large parametric laboratory study including more than 200 long-duration model tests. The study addresses both the wave forces imposed on the breakwater crown wall as well as the performance of the structure in reducing the wave overtopping. The testing...

  17. Earth Pressure on Tunnel Crown

    DEFF Research Database (Denmark)

    Andersen, Lars

    Two different analyses have been carried out in order to find the vertical earth pressure, or overburden pressure, at the crown of a tunnel going through a dike. Firstly, a hand calculation is performed using a simple dispersion of the stresses over depth. Secondly, the finite‐element program...

  18. The extraction of alkali metal picrates with dibenzo-18-crown-6

    International Nuclear Information System (INIS)

    Sadakane, Akira; Toei, Kyoji; Iwachido, Tadashi.

    1975-01-01

    The distribution of alkali metal picrate complexes of macrocyclic polyether (dibenzo-18-crown-6) between water and benzene was investigated. The polyether-cation complexes were found to be of a 1:1 stoichiometry. The formation of 2:1 complexes was recognized for Rb and Cs in a large excess of the polyether. The extractability of complex cation-picrate ion-pairs decreases in this sequence: K>Rb>Cs>Na>Li. The values of the extraction constants (log Ksub(ex)) were determined to be 4.65, 3.75, and 3.07 for K, Rb, and Cs compounds respectively. The thermodynamic quantities for the extraction process were calculated from the change in the extraction constants with the temperature. The extraction reactions are all exothermic, accompanied by an entropy decrease. (auth.)

  19. Digital photo monitoring for tree crown

    Science.gov (United States)

    Neil Clark; Sang-Mook Lee

    2007-01-01

    Assessing change in the amount of foliage within a tree’s crown is the goal of crown transparency estimation, a component in many forest health assessment programs. Many sources of variability limit analysis and interpretation of crown condition data. Increased precision is needed to detect more subtle changes that are important for detection of health problems....

  20. A strategy for the diversity-oriented synthesis of macrocyclic scaffolds using multidimensional coupling

    DEFF Research Database (Denmark)

    Beckmann, Henning S G; Nie, Feilin; Hagerman, Caroline E

    2013-01-01

    the coupling reaction. We applied this step-efficient approach in a DOS of a library that consisted of 73 macrocyclic compounds based around 59 discrete scaffolds. The macrocycles prepared cover a broad range of different molecular shapes, as illustrated by principal moment-of-inertia analysis...

  1. Toward understanding macrocycle specificity of iron on the dioxygen-binding ability: a theoretical study.

    Science.gov (United States)

    Sun, Yong; Chen, Kexian; Jia, Lu; Li, Haoran

    2011-08-14

    In an effort to examine the interaction between dioxygen and iron-macrocyclic complexes, and to understand how this interaction was affected by those different macrocyclic ligands, dioxygen binding with iron-porphyrin, iron-phthalocyanine, iron-dibenzotetraaza[14]annulene, and iron-salen complexes is investigated by means of quantum chemical calculations utilizing Density Functional Theory (DFT). Based on the analysis of factors influencing the corresponding dioxygen binding process, it showed that different macrocyclic ligands possess different O-O bond distances, and different electronic configurations for the bound O(2) and non-aromatic macrocyclic ligands favor dioxygen activation. Furthermore, the smaller the energy gap between the HOMO of iron-macrocyclic complexes and the LUMO of dioxygen, the more active the bound O(2) becomes, with a longer O-O bond distance and a shorter Fe-O bond length.

  2. Preparation and characterization of electroluminescent devices based on complexes of β-diketonates of Tb3+, Eu3+, Gd3+ ions with macrocyclic ligands and UO22+ films

    International Nuclear Information System (INIS)

    Gibelli, Edison Bessa

    2010-01-01

    Complexes containing Rare Earth ions are of great interest in the manufacture of electro luminescent devices as organic light emitting devices (OLED). These devices, using rare earth trivalent ions (TR 3+ ) as emitting centers, show high luminescence with extremely fine spectral bands due to the structure of their energy levels, long life time and high quantum efficiency. This work reports the preparation of Rare Earth β-diketonate complexes (Tb 3+ , Eu 3+ and Gd 3+ ) and (tta - thenoyltrifluoroacetonate and acac - acetylacetonate) containing a ligand macrocyclic crown ether (DB18C6 - dibenzo18coroa6) and polymer films of UO 2 2+ . The materials were characterized by complexometric titration with EDTA, CH elemental analysis, near infrared absorption spectroscopy, thermal analysis, X-ray diffraction (powder method) and luminescence spectroscopy. For manufacturing the OLED it was used the technique of deposition of thin films by physical vapor (PVD, Physical Vapor Deposition). (author)

  3. STABILIZATION OF UNUSUAL SUBSTRATE COORDINATION MODES IN DINUCLEAR MACROCYCLIC COMPLEXES

    Directory of Open Access Journals (Sweden)

    Vasile Lozan

    2010-06-01

    Full Text Available The steric protection offered by the macrobinucleating hexaazaditiophenolate ligand (L allows for the preparation of the first stable dinuclear nickel(II borohydride bridged complex, which reacts rapidly with elemental sulphur producing a tetranuclear nickel(II complex [{(LNi2}2(μ-S6]2+ bearing a helical μ4-hexa- sulfide ligand. The [(LCoII 2]2+ fragment have been able to trap a monomethyl orthomolybdate in the binding pocket. Unusual coordination modes of substrate in dinuclear macrocyclic compounds was demonstrated.

  4. Macrocyclic extractants for separating Am(III)/Ln(III)

    International Nuclear Information System (INIS)

    Ludwig, R.; Nguyen, T.K.D.; Kunogi, K.; Tachimori, Shoichi

    1999-01-01

    The extraction of trivalent f-elements by calix(n)arene-type macrocyclic ligands increases in the order n=4, 8, 6 corresponding to the balance between cavity size, molecular flexibility, and number of donor atoms. Introduction of mixed functionalities into calix(6)arenes, e.g. carboxylic acid and amide groups, results in better extractability of actinides compared with lanthanides. For calix(4)arenes, such a different extractability could not be observed. Furthermore, the effects of solvent composition with respect to a modifier and of the aqueous phase composition were investigated. (author)

  5. Natural and Synthetic Macrocyclic Inhibitors of the Histone Deacetylase Enzymes

    DEFF Research Database (Denmark)

    Maolanon, Alex; Kristensen, Helle; Leman, Luke

    2017-01-01

    Inhibition of histone deacetylase (HDAC) enzymes has emerged as a target for development of cancer chemotherapy. Four compounds have gained approval for clinical use by the Food and Drug Administration (FDA) in the US, and several are currently in clinical trials. However, none of these compounds...... HDAC enzymes may hold an advantage over traditional hydroxamic acid-containing inhibitors, which rely on chelation to the conserved active site zinc ion. Here, we review the literature on macrocyclic HDAC inhibitors obtained from natural sources and structure-activity relationship studies inspired...

  6. Macrocyclic ligands and their use in chemical separations

    International Nuclear Information System (INIS)

    Izatt, R.M.; Bradshaw, J.S.; Bruening, R.L.; Krakowiak, K.E.; Tarbet, B.J.

    1993-01-01

    Macrocyclic chemistry has had a phenomenal growth curve during the past three decades (Izatt et al.). Interest in this field was catalyzed by Pedersen's report of the synthesis and partial characterization of a large number of novel cyclic polyethers. The unusual affinity of these new compounds for and selectivity among alkali metal cations was noted (Pedersen) and quantitated (Izatt et al.). A 1987 National Academy of Science publication on separations listed three high priority needs in the separations field (King). These were to develop highly selective reagents capable of discriminating among similar chemical species, reagents capable of concentrating trace amounts of solutes even in the presence of large excesses of matrix solutes, and reagents capable of removing solutes from large quantities of solvent. Certain macrocycles offer the promise of being successful in achieving all three of these goals. This promise arises from their high selectivity for particular cations in various series of closely related cations, their large affinities for particular cations, and the ease with which they can be modified to meet particular needs inherent to chemical separations

  7. Solar Thermal Energy Storage in a Photochromic Macrocycle.

    Science.gov (United States)

    Vlasceanu, Alexandru; Broman, Søren L; Hansen, Anne S; Skov, Anders B; Cacciarini, Martina; Kadziola, Anders; Kjaergaard, Henrik G; Mikkelsen, Kurt V; Nielsen, Mogens Brøndsted

    2016-07-25

    The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA-DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF-VHF). A stepwise energy release over two sequential ring-closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long-term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. ''Crown molecules'' for separating cesium

    International Nuclear Information System (INIS)

    Dozol, J.F.; Lamare, V.

    2002-01-01

    After the minor actinides, the second category of radionuclides that must be isolated to optimize nuclear waste management concerns fission products, especially two cesium isotopes. If the cesium-135 isotope could be extracted, it could subsequently be transmuted or conditioned using a tailor-made process. Eliminating the 137 isotope from reprocessing and nuclear facility-dismantling waste would allow to dispose of most of this waste in near-surface facilities, and simply process the small remaining quantity containing long-lived elements. CEA research teams and their international partners have thought up crown molecules that could be used to pick out the cesium and meet these objectives. (authors)

  9. All-ceramic crowns: bonding or cementing?

    Science.gov (United States)

    Pospiech, Peter

    2002-12-01

    Despite the wide variety of all-ceramic systems available today, the majority of dental practitioners hesitate to recommend and insert all-ceramic crowns. This article regards the nature of the ceramic materials, the principles of bonding and adhesion, and the clinical problems of the acid-etch technique for crowns. Advantages and disadvantages are discussed, and the influences of different factors on the strength of all-ceramic crowns are presented. Finally, the conclusion is drawn that conventional cementing of all-ceramic crowns is possible when the specific properties of the ceramics are taken into consideration.

  10. Pericoronal radiolucency associated with incomplete crown

    International Nuclear Information System (INIS)

    Nah, Kyung Soo

    2013-01-01

    The author experienced 8 cases of pericoronal radiolucency involving an incomplete tooth crown that had not developed to form the cemento-enamel junction, and the underdeveloped crown sometimes appeared to be floating within the radiolucency radiographically. The first impression was that these cystic lesions had odontogenic keratocysts, but half of them turned out to be dentigerous cysts histopathologically. There has been no report concerning odontogenic cysts involving an incompletely developed crown. The purpose of this paper is to report that dentigerous cysts may develop before the completion of the cemento-enamel junction of a developing crown.

  11. Pericoronal radiolucency associated with incomplete crown

    Energy Technology Data Exchange (ETDEWEB)

    Nah, Kyung Soo [Dept. of Oral and Maxillofacial Radiology, School of Dentistry, Pusan National University, Yangsan (Korea, Republic of)

    2013-12-15

    The author experienced 8 cases of pericoronal radiolucency involving an incomplete tooth crown that had not developed to form the cemento-enamel junction, and the underdeveloped crown sometimes appeared to be floating within the radiolucency radiographically. The first impression was that these cystic lesions had odontogenic keratocysts, but half of them turned out to be dentigerous cysts histopathologically. There has been no report concerning odontogenic cysts involving an incompletely developed crown. The purpose of this paper is to report that dentigerous cysts may develop before the completion of the cemento-enamel junction of a developing crown.

  12. Lanthanide paramagnetic probes for NMR spectroscopic studies of fast molecular conformational dynamics and temperature control. Effective six-site proton exchange in 18-crown-6 by exchange spectroscopy.

    Science.gov (United States)

    Babailov, Sergey P

    2012-02-06

    (1)H and (13)C NMR measurements are reported for the CDCl(3) and CD(2)Cl(2) solutions of [La(18-crown-6)(NO(3))(3)] (I), [Pr(18-crown-6) (NO(3))(3)] (II), [Ce(18-crown-6)(NO(3))(3)] (III), and [Nd(18-crown-6)(NO(3))(3)] (IV) complexes. Temperature dependencies of the (1)H NMR spectra of paramagnetic II-IV have been analyzed using the dynamic NMR (DNMR) methods for six-site exchange. Two types of conformational dynamic processes were identified (the first one is conditioned by interconversion of complex enantiomeric forms and pseudorotation of a macrocycle molecule upon the C(2) symmetry axis; the second one is conditioned by macrocycle molecule inversion). Application of exchange spectroscopy (2D-EXSY) of DNMR for investigation of this dynamic system (II-IV) simplifies the assignment of the NMR signals and represents the first experimental study of multisite exchange. In the present work, the methodology of paramagnetic 4f (Ce, Pr, and Nd) probe applications for the study of free-energy, enthalpy, and entropy changes in chemical exchange processes, as well as the advantages of this method in a comparison with DNMR studies of diamagnetic substances, is discussed. In particular, as a result of paramagnetic chemical shifts in 4f complexes, the range of measurable rate constants expands considerably compared to the analogous range in diamagnetic compounds. Coordination compounds investigated in the paper represent new types of thermometric NMR sensors and lanthanide paramagnetic probes for in situ temperature control in solution.

  13. Fracture-resistant monolithic dental crowns.

    Science.gov (United States)

    Zhang, Yu; Mai, Zhisong; Barani, Amir; Bush, Mark; Lawn, Brian

    2016-03-01

    To quantify the splitting resistance of monolithic zirconia, lithium disilicate and nanoparticle-composite dental crowns. Fracture experiments were conducted on anatomically-correct monolithic crown structures cemented to standard dental composite dies, by axial loading of a hard sphere placed between the cusps. The structures were observed in situ during fracture testing, and critical loads to split the structures were measured. Extended finite element modeling (XFEM), with provision for step-by-step extension of embedded cracks, was employed to simulate full failure evolution. Experimental measurements and XFEM predictions were self-consistent within data scatter. In conjunction with a fracture mechanics equation for critical splitting load, the data were used to predict load-sustaining capacity for crowns on actual dentin substrates and for loading with a sphere of different size. Stages of crack propagation within the crown and support substrate were quantified. Zirconia crowns showed the highest fracture loads, lithium disilicate intermediate, and dental nanocomposite lowest. Dental nanocomposite crowns have comparable fracture resistance to natural enamel. The results confirm that monolithic crowns are able to sustain high bite forces. The analysis indicates what material and geometrical properties are important in optimizing crown performance and longevity. Copyright © 2015 Academy of Dental Materials. All rights reserved.

  14. Coast redwood live crown and sapwood

    Science.gov (United States)

    John-Pascal Berrill; Jesse L. Deffress; Jessica M. Engle

    2012-01-01

    Understanding crown rise and sapwood taper will help meet management objectives such as producing long branch-free boles for clear wood and old-growth restoration, or producing sawlogs with a high proportion of heartwood. Coast redwood (Sequoia sempervirens) tree crown ratio data were collected 20 years after partial harvesting in a 65-year-old second growth stand....

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

    KAUST Repository

    Ji, Xiaofan; Wu, Ren-Tsung; Long, Lingliang; Guo, Chenxing; Khashab, Niveen M.; Huang, Feihe; Sessler, Jonathan L.

    2018-01-01

    Reported here is a hydrogel-forming polymer network that contains a water-soluble tetracationic macrocycle. Upon immersion of this polymer network in aqueous solutions containing various inorganic and organic salts, changes in the physical

  16. Versatile Multicomponent Reaction Macrocycle Synthesis Using α-Isocyano-ω-carboxylic Acids

    NARCIS (Netherlands)

    Liao, George P; Abdelraheem, Eman M M; Neochoritis, Constantinos G; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; McGowan, David C; Dömling, Alexander

    2015-01-01

    The direct macrocycle synthesis of α-isocyano-ω-carboxylic acids via an Ugi multicomponent reaction is introduced. This multicomponent reaction (MCR) protocol differs by being especially short, convergent, and versatile, giving access to 12-22 membered rings.

  17. Towards tumour targeting with copper-radiolabelled macrocycle-antibody conjugates

    International Nuclear Information System (INIS)

    Morphy, J.R.; Parker, David; Kataky, Ritu

    1989-01-01

    Tetraaza-macrocycles covalently attached to a monoclonal antibody may be efficiently radiolabelled with 64 Cu or 67 Cu at pH4, minimising non-specific binding to the protein, giving a kinetically stable conjugate in vivo. (author)

  18. Complexation of the strontium cation with a macrocyclic lactam receptor: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Vaňura, P.

    2016-01-01

    Roč. 214, FEB 2016 (2016), s. 171-174 ISSN 0167-7322 Institutional support: RVO:61388955 Keywords : strontium cation * macrocyclic lactam receptor Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.648, year: 2016

  19. Acetone-Linked Peptides: A Convergent Approach for Peptide Macrocyclization and Labeling.

    Science.gov (United States)

    Assem, Naila; Ferreira, David J; Wolan, Dennis W; Dawson, Philip E

    2015-07-20

    Macrocyclization is a broadly applied approach for overcoming the intrinsically disordered nature of linear peptides. Herein, it is shown that dichloroacetone (DCA) enhances helical secondary structures when introduced between peptide nucleophiles, such as thiols, to yield an acetone-linked bridge (ACE). Aside from stabilizing helical structures, the ketone moiety embedded in the linker can be modified with diverse molecular tags by oxime ligation. Insights into the structure of the tether were obtained through co-crystallization of a constrained S-peptide in complex with RNAse S. The scope of the acetone-linked peptides was further explored through the generation of N-terminus to side chain macrocycles and a new approach for generating fused macrocycles (bicycles). Together, these studies suggest that acetone linking is generally applicable to peptide macrocycles with a specific utility in the synthesis of stabilized helices that incorporate functional tags. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Macrocyclic bis(ureas as ligands for anion complexation

    Directory of Open Access Journals (Sweden)

    Claudia Kretschmer

    2014-08-01

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

  1. Macrocyclic bis-thioureas catalyze stereospecific glycosylation reactions.

    Science.gov (United States)

    Park, Yongho; Harper, Kaid C; Kuhl, Nadine; Kwan, Eugene E; Liu, Richard Y; Jacobsen, Eric N

    2017-01-13

    Carbohydrates are involved in nearly all aspects of biochemistry, but their complex chemical structures present long-standing practical challenges to their synthesis. In particular, stereochemical outcomes in glycosylation reactions are highly dependent on the steric and electronic properties of coupling partners; thus, carbohydrate synthesis is not easily predictable. Here we report the discovery of a macrocyclic bis-thiourea derivative that catalyzes stereospecific invertive substitution pathways of glycosyl chlorides. The utility of the catalyst is demonstrated in the synthesis of trans-1,2-, cis-1,2-, and 2-deoxy-β-glycosides. Mechanistic studies are consistent with a cooperative mechanism in which an electrophile and a nucleophile are simultaneously activated to effect a stereospecific substitution reaction. Copyright © 2017, American Association for the Advancement of Science.

  2. Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

    Directory of Open Access Journals (Sweden)

    Margherita De Rosa

    2018-04-01

    Full Text Available In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively the substrates isolating they from the reaction environment. In addition, the synthetic versatilities of these macrocycles permits to introduce useful functional groups in close proximity of the hydrophobic binding sites. Regarding the cyclodextrins (CDs, we have here reviewed the their most recent uses as organocatalysts for the synthesis of heterocyclic compounds, in multi-component reactions and in carbon-carbon bond forming reactions. Examples have been reported in which CD catalysts are able to drive the regiochemistry of common organic reactions. In addition, cyclodextrins bearing catalytically active chiral groups, have shown excellent enantioselectivity in the catalysis of organic reactions. Recently reported results have shown that calixarene derivatives are able to accelerate organic reaction under “on-water” conditions with a significant selectivity toward the reactants. Under “on-water conditions” the hydrophobic effect, induced by insoluble calixarene derivatives, forces the reactants and the catalyst to aggregate and thus accelerating the reaction between them thanks to an amplification of weak secondary interactions. Regarding the use of water-soluble calixarene organocatalysts, we have here reviewed their role in the acceleration of

  3. Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

    Science.gov (United States)

    De Rosa, Margherita; La Manna, Pellegrino; Talotta, Carmen; Soriente, Annunziata; Gaeta, Carmine; Neri, Placido

    2018-04-01

    In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively the substrates isolating they from the reaction environment. In addition, the synthetic versatilities of these macrocycles permits to introduce useful functional groups in close proximity of the hydrophobic binding sites. Regarding the cyclodextrins (CDs), we have here reviewed the their most recent uses as organocatalysts for the synthesis of heterocyclic compounds, in multi-component reactions and in carbon-carbon bond forming reactions. Examples have been reported in which CD catalysts are able to drive the regiochemistry of common organic reactions. In addition, cyclodextrins bearing catalytically active chiral groups, have shown excellent enantioselectivity in the catalysis of organic reactions. Recently reported results have shown that calixarene derivatives are able to accelerate organic reaction under "on-water" conditions with a significant selectivity toward the reactants. Under "on-water conditions" the hydrophobic effect, induced by insoluble calixarene derivatives, forces the reactants and the catalyst to aggregate and thus accelerating the reaction between them thanks to an amplification of weak secondary interactions. Regarding the use of water-soluble calixarene organocatalysts, we have here reviewed their role in the acceleration of common organic reactions.

  4. C-84 Selective Porphyrin Macrocycle with an Adaptable Cavity Constructed Through Alkyne Metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C. X.; Long, H.; Zhang, W.

    2012-06-21

    A bisporphyrin macrocycle was constructed from a porphyrin-based diyne monomer in one step through alkyne metathesis. The fullerene binding studies (C{sub 60}, C{sub 70} and C{sub 84}) showed the highest binding affinity of the macrocycle for C{sub 84}, which is in great contrast to its bisporphyrin four-armed cage analogue that showed the strongest binding with C{sub 70}.

  5. Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

    International Nuclear Information System (INIS)

    Kim, Taehyung; Kim, Ju Chang; Lough, Alan J.

    2013-01-01

    Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

  6. How Secondary and Tertiary Amide Moieties are Molecular Stations for Dibenzo-24-crown-8 in [2]Rotaxane Molecular Shuttles?

    Science.gov (United States)

    Riss-Yaw, Benjamin; Morin, Justine; Clavel, Caroline; Coutrot, Frédéric

    2017-11-21

    Interlocked molecular machines like [2]rotaxanes are intriguing aesthetic molecules. The control of the localization of the macrocycle, which surrounds a molecular axle, along the thread leads to translational isomers of very different properties. Although many moieties have been used as sites of interactions for crown ethers, the very straightforwardly obtained amide motif has more rarely been envisaged as molecular station. In this article, we report the use of secondary and tertiary amide moieties as efficient secondary molecular station in pH-sensitive molecular shuttles. Depending on the N -substitution of the amide station, and on deprotonation or deprotonation-carbamoylation, the actuation of the molecular machinery differs accordingly to very distinct interactions between the axle and the DB24C8.

  7. High yielding synthesis of 2,2′-bipyridine macrocycles, versatile intermediates in the synthesis of rotaxanes

    OpenAIRE

    Lewis, J. E. M.; Bordoli, R. J.; Denis, M.; Fletcher, C. J.; Galli, M.; Neal, E. A.; Rochette, E. M.; Goldup, S. M.

    2016-01-01

    We present an operationally simple approach to 2,2?-bipyridine macrocycles. Our method uses simple starting materials to produce these previously hard to access rotaxane precursors in remarkable yields (typically >65%) across a range of scales (0.1–5 mmol). All of the macrocycles reported are efficiently converted (>90%) to rotaxanes under AT-CuAAC conditions. With the requisite macrocycles finally available in sufficient quantities, we further demonstrate their long term utility throug...

  8. Macrocyclic ligand decorated ordered mesoporous silica with large-pore and short-channel characteristics for effective separation of lithium isotopes: synthesis, adsorptive behavior study and DFT modeling.

    Science.gov (United States)

    Liu, Yuekun; Liu, Fei; Ye, Gang; Pu, Ning; Wu, Fengcheng; Wang, Zhe; Huo, Xiaomei; Xu, Jian; Chen, Jing

    2016-10-18

    Effective separation of lithium isotopes is of strategic value which attracts growing attention worldwide. This study reports a new class of macrocyclic ligand decorated ordered mesoporous silica (OMS) with large-pore and short-channel characteristics, which holds the potential to effectively separate lithium isotopes in aqueous solutions. Initially, a series of benzo-15-crown-5 (B15C5) derivatives containing different electron-donating or -withdrawing substituents were synthesized. Extractive separation of lithium isotopes in a liquid-liquid system was comparatively studied, highlighting the effect of the substituent, solvent, counter anion and temperature. The optimal NH 2 -B15C5 ligands were then covalently anchored to a short-channel SBA-15 OMS precursor bearing alkyl halides via a post-modification protocol. Adsorptive separation of the lithium isotopes was fully investigated, combined with kinetics and thermodynamics analysis, and simulation by using classic adsorption isotherm models. The NH 2 -B15C5 ligand functionalized OMSs exhibited selectivity to lithium ions against other alkali metal ions including K(i). Additionally, a more efficient separation of lithium isotopes could be obtained at a lower temperature in systems with softer counter anions and solvents with a lower dielectric constant. The highest value separation factor (α = 1.049 ± 0.002) was obtained in CF 3 COOLi aqueous solution at 288.15 K. Moreover, theoretical computation based on the density functional theory (DFT) was performed to elucidate the complexation interactions between the macrocyclic ligands and lithium ions. A suggested mechanism involving an isotopic exchange equilibrium was proposed to describe the lithium isotope separation by the functionalized OMSs.

  9. Scalpel Depigmentation and Surgical Crown Lengthening to ...

    African Journals Online (AJOL)

    level of the apices of the six maxillary anterior teeth. Maxillary canines and ... requires osseous resection surgeries whereas excessive gingival display due to ... this case included complete oral prophylaxis along aesthetic crown lengthening ...

  10. Crown-rise and crown-length dynamics: applications to loblolly pine

    Science.gov (United States)

    Harry T. Valentine; Ralph L. Amateis; Jeffrey H. Gove; Annikki. Makela

    2013-01-01

    The original crown-rise model estimates the average height of a crown-base in an even-aged mono-species stand of trees. We have elaborated this model to reduce bias and prediction error, and to also provide crown-base estimates for individual trees. Results for the latter agree with a theory of branch death based on resource availability and allocation.We use the...

  11. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  12. [Tl(III)(dota)](-): An Extraordinarily Robust Macrocyclic Complex.

    Science.gov (United States)

    Fodor, Tamás; Bányai, István; Bényei, Attila; Platas-Iglesias, Carlos; Purgel, Mihály; Horváth, Gábor L; Zékány, László; Tircsó, Gyula; Tóth, Imre

    2015-06-01

    The X-ray structure of {C(NH2)3}[Tl(dota)]·H2O shows that the Tl(3+) ion is deeply buried in the macrocyclic cavity of the dota(4-) ligand (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) with average Tl-N and Tl-O distances of 2.464 and 2.365 Å, respectively. The metal ion is directly coordinated to the eight donor atoms of the ligand, which results in a twisted square antiprismatic (TSAP') coordination around Tl(3+). A multinuclear (1)H, (13)C, and (205)Tl NMR study combined with DFT calculations confirmed the TSAP' structure of the complex in aqueous solution, which exists as the Λ(λλλλ)/Δ(δδδδ) enantiomeric pair. (205)Tl NMR spectroscopy allowed the protonation constant associated with the protonation of the complex according to [Tl(dota)](-) + H(+) ⇆ [Tl(Hdota)] to be determined, which turned out to be pK(H)Tl(dota) = 1.4 ± 0.1. [Tl(dota)](-) does not react with Br(-), even when using an excess of the anion, but it forms a weak mixed complex with cyanide, [Tl(dota)](-) + CN(-) ⇆ [Tl(dota)(CN)](2-), with an equilibrium constant of Kmix = 6.0 ± 0.8. The dissociation of the [Tl(dota)](-) complex was determined by UV-vis spectrophotometry under acidic conditions using a large excess of Br(-), and it was found to follow proton-assisted kinetics and to take place very slowly (∼10 days), even in 1 M HClO4, with the estimated half-life of the process being in the 10(9) h range at neutral pH. The solution dynamics of [Tl(dota)](-) were investigated using (13)C NMR spectroscopy and DFT calculations. The (13)C NMR spectra recorded at low temperature (272 K) point to C4 symmetry of the complex in solution, which averages to C4v as the temperature increases. This dynamic behavior was attributed to the Λ(λλλλ) ↔ Δ(δδδδ) enantiomerization process, which involves both the inversion of the macrocyclic unit and the rotation of the pendant arms. According to our calculations, the arm-rotation process limits the Λ(λλλλ) ↔

  13. 4-Bromoanilinium perchlorate 18-crown-6 clathrate

    Directory of Open Access Journals (Sweden)

    Min Guo

    2010-11-01

    Full Text Available The reaction of 4-bromoaniline, 18-crown-6, and perchloric acid in methanol yields the title compound, C6H7BrN+·ClO4−·C12H24O6, in which the protonated –NH3+ group forms three bifurcated N—H...O hydrogen bonds to the O atoms of the crown ether.

  14. Assessment of crown angulations, crown inclinations, and tooth size discrepancies in a South Indian population

    Directory of Open Access Journals (Sweden)

    Geeta Maruti Doodamani

    2011-01-01

    Full Text Available Aims and Objective: The aim of this study was to assess crown angulations, crown inclinations, and tooth size discrepancy in a sample population from Davangere, South India. Materials and Methods: One hundred adults (50 male and 50 female of age 18-30 years, with Angle′s class I ideal occlusion and balanced profiles, were selected for the study. Study models were prepared and crown angulations and crown inclinations were measured using a customized protractor device. Bolton′s analysis was used to measure the tooth size discrepancies. Results: Maxillary and mandibular teeth had less crown angulations. Maxillary and mandibular incisors and maxillary molars showed increased crown inclinations, whereas mandibular molars and premolars had less crown inclinations than the original Andrews sample. The mean maxillary and mandibular tooth size ratios, overall and anterior, were similar to Bolton′s ratios. Conclusions: The finding of this study indicates that there are possible racial and ethnic factors contributing to variations in crown angulations and crown inclinations.

  15. Experimental and numerical modeling of shrub crown fire initiation

    Science.gov (United States)

    Watcharapong Tachajapong; Jesse Lozano; Shakar Mahalingam; Xiangyang Zhou; David Weise

    2009-01-01

    The transition of fire from dry surface fuels to wet shrub crown fuels was studied using laboratory experiments and a simple physical model to gain a better understanding of the transition process. In the experiments, we investigated the effects of varying vertical distances between surface and crown fuels (crown base height), and of the wind speed on crown fire...

  16. Preformed crowns for decayed primary molar teeth.

    Science.gov (United States)

    Innes, Nicola P T; Ricketts, David; Chong, Lee Yee; Keightley, Alexander J; Lamont, Thomas; Santamaria, Ruth M

    2015-12-31

    Crowns for primary molars are preformed and come in a variety of sizes and materials to be placed over decayed or developmentally defective teeth. They can be made completely of stainless steel (know as 'preformed metal crowns' or PMCs), or to give better aesthetics, may be made of stainless steel with a white veneer cover or made wholly of a white ceramic material. In most cases, teeth are trimmed for the crowns to be fitted conventionally using a local anaesthetic. However, in the case of the Hall Technique, PMCs are pushed over the tooth with no local anaesthetic, carious tissue removal or tooth preparation. Crowns are recommended for restoring primary molar teeth that have had a pulp treatment, are very decayed or are badly broken down. However, few dental practitioners use them in clinical practice. This review updates the original review published in 2007. Primary objectiveTo evaluate the clinical effectiveness and safety of all types of preformed crowns for restoring primary teeth compared with conventional filling materials (such as amalgam, composite, glass ionomer, resin modified glass ionomer and compomers), other types of crowns or methods of crown placement, non-restorative caries treatment or no treatment. Secondary objectiveTo explore whether the extent of decay has an effect on the clinical outcome of primary teeth restored with all types of preformed crowns compared with those restored with conventional filling materials. We searched the following electronic databases: Cochrane Oral Health Group Trials Register (to 21 January 2015), Cochrane Central Register of Controlled Trials (CENTRAL; The Cochrane Library, 2014, Issue 12), MEDLINE via Ovid (1946 to 21 January 2015) and EMBASE via Ovid (1980 to 21 January 2015). We searched the US National Institutes of Health Trials Register (http://clinicaltrials.gov) and the World Health Organization (WHO) International Clinical Trials Registry Platform for ongoing trials and Open Grey for grey literature (to

  17. Dissociation kinetics of acyclic and macrocyclic polyaminopolycarboxylate complexes of yttrium

    International Nuclear Information System (INIS)

    Pathak, P.N.; Manchanda, V.K.

    2000-01-01

    Dissociation kinetics of Y III complexes of a linear as well as two macrocyclic polyaminopolycarboxylates, ethylenediamine diacetic acid (EDDA), 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid (K21DA) and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (K22DA) have been studied at a constant ionic strength (0.1 M) under varying (H + ) and temperatures. Cu II ion acts as the scavenger of the free ligand. Dissociation rate of Y III -K21DA is insensitive to Cu II and acetate (used as buffer anion) concentrations. Kinetic stability of the three complexes follow the order : Y III -K22DA>Y III -K21DA>Y III -EDDA. Enthalpies of activation for K21DA and K22DA complexes of Y III are also evaluated. Thermodynamic stability constant (log K) for Y III -K22DA complex is 10.81 ± 0.04. (author)

  18. An investigation of crown fuel bulk density effects on the dynamics of crown fire initiation in shrublands

    Science.gov (United States)

    Watcharapong Tachajapong; Jesse Lozano; Shankar Mahalingam; Xiangyang Zhou; David R. Weise

    2008-01-01

    Crown fire initiation is studied by using a simple experimental and detailed physical modeling based on Large Eddy Simulation (LES). Experiments conducted thus far reveal that crown fuel ignition via surface fire occurs when the crown base is within the continuous flame region and does not occur when the crown base is located in the hot plume gas region of the surface...

  19. Extraction separation of lithium isotopes with crown-ethers

    International Nuclear Information System (INIS)

    Tsivadze, A.Yu.; Demin, S.V.; Levkin, A.V.; Zhilov, V.I.; Nikol'skij, S.F.; Knyazev, D.A.

    1990-01-01

    By the method of extraction chromatography lithium isotope separation coefficients are measured during chemical isotope exchange between lithium aquocomplex and its complex in chloroform with crown-ethers: benzo-15-crown-5, 15crown-5, dicyclohexano-18-crown-6 and dibenzo-18-crown-6. Lithium perchlorate and trichloroacetate are the salts extracted. Values of 6 Li/ 7 Li isotope separation are 1.0032-1.020

  20. COMPARSION EFFECTIVENES METHODS REPEIR CROWN TEETH IN DOGS

    OpenAIRE

    CHOOHNO V.S.

    2008-01-01

    Methods of dogs’ crown teeth restoration with using of anchor pin with light curable composite, glass fiber pin with light curable composite, stump crown with prosthetic crown were approved. Their effectiveness was compared. Greater reliability was shown by methods of stump crown with prosthetic crown, when using of which there was no that restoration damage in all cases, but there was no cosmetics effect. Restoration methods with using anchor pin with light curable composite and glass fiber ...

  1. Urban Crowns: crown analysis software to assist in quantifying urban tree benefits

    Science.gov (United States)

    Matthew F. Winn; Sang-Mook Lee Bradley; Philip A. Araman

    2010-01-01

    UrbanCrowns is a Microsoft® Windows®-based computer program developed by the U.S. Forest Service Southern Research Station. The software assists urban forestry professionals, arborists, and community volunteers in assessing and monitoring the crown characteristics of urban trees (both deciduous and coniferous) using a single side-view digital photograph. Program output...

  2. Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism.

    Science.gov (United States)

    Vollmeyer, Joscha; Eberhagen, Friederike; Höger, Sigurd; Jester, Stefan-S

    2014-01-01

    Three shape-persistent naphthylene-phenylene-acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

  3. Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

    Directory of Open Access Journals (Sweden)

    Joscha Vollmeyer

    2014-11-01

    Full Text Available Three shape-persistent naphthylene–phenylene–acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

  4. Zn2+ -Ion Sensing by Fluorescent Schiff Base Calix[4]arene Macrocycles.

    Science.gov (United States)

    Ullmann, Steve; Schnorr, René; Handke, Marcel; Laube, Christian; Abel, Bernd; Matysik, Jörg; Findeisen, Matthias; Rüger, Robert; Heine, Thomas; Kersting, Berthold

    2017-03-17

    A macrocyclic ligand (H 2 L) containing two o,o'-bis(iminomethyl)phenol and two calix[4]arene head units has been synthesized and its coordination chemistry towards divalent Ni and Zn investigated. The new macrocycle forms complexes of composition [ML] (M=Zn, M=Ni) and [ZnL(py) 2 ], which were characterized by elemental analysis; IR, UV/Vis, and NMR spectroscopy; electrospray ionization mass spectrometry (ESI-MS); and X-ray crystallography (for [ZnL(py) 2 ] and [NiL]). H 2 L allows the sensitive optical detection of Zn 2+ among a series of biologically relevant metal ions by a dual fluorescence enhancement/quenching effect in solution. The fluorescence intensity of the macrocycle increases by a factor of ten in the presence of Zn 2+ with a detection limit in the lower nanomolar region. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Macrocyclic ligands for uranium complexation. Final report, August 1, 1986--March 31, 1993

    International Nuclear Information System (INIS)

    Potts, K.T.

    1993-01-01

    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ions, have been prepared and their complexation of the uranyl ions evaluated. The ligating atoms, either oxygen or sulfur, were part of acylurea, biuret or thiobiuret subunits with alkane chains or pyridine units completing the macrocyclic periphery. These macrocycles with only partial preorganization formed uranyl complexes in solution but no crystalline complexes were isolated. Refinement of the cavity diameter by variation of the peripheral functional groups is currently studied to achieve an optimized cavity diameter of 4.7--5.2 angstrom. Acyclic ligands containing the same ligating atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex (stability constant log K = 10.7) whose structure was established by X-ray data. This complex underwent a facile, DMSO-induced rearrangement to a 2:1 uranyl-ligand complex whose structure was also established by X-ray data. The intermediates to the macrocycles all behaved as excellent ligands for the complexation of transition metals. Acylthiourea complexes of copper and nickel as well as intermolecular, binuclear copper and nickel complexes of bidentate carbonyl thioureas formed readily and their structures were established in several representative instances by X-ray structural determinations. Tetradentate bis(carbonylthioureas) were found to be very efficient selective reagents for the complexation of copper in the presence of nickel ions. Several preorganized macrocycles were also prepared but in most instances these macrocycles underwent ring-opening under complexation conditions

  6. Retrospective Study of Retention of Stainless Steel Crowns and Pre-veneered Crowns on Primary Anterior Teeth.

    Science.gov (United States)

    Lopez-Loverich, Angela M; Garcia, Maria Minerva; Donly, Kevin J

    2015-01-01

    The purpose of this retrospective chart review was to explore the retention of anterior pre-veneered stainless steel crowns (NuSmile) and conventional stainless steel crowns (3M ESPE) placed on primary anterior teeth. Records for children were reviewed over four years using the electronic record system axiUm. Data collected included child's age at time of crown placement, date of placement, tooth number, type of crown, patient behavior, treatment environment, provider type, crown presence, absence, and cementation success or failure at subsequent recall visits. A total of 637 anterior crowns in children treated with either or both crown types met this study's inclusion criteria. Of these crowns, 483 were NuSmile Signature crowns and 154 were stainless steel crowns. There was a nine percent failure rate for the NuSmile Signature crowns and a seven percent failure rate for the stainless steel crowns. There was no statistically significant difference in crown retention rates between the two groups (P<0.05). A full-coverage restoration that can follow the lifespan of the primary anterior dentition in high-risk children is needed. The results from this study indicate good crown retention rates for both crown types with no statistically significant difference between them (P<0.05).

  7. Exploring the Binding of Barbital to a Synthetic Macrocyclic Receptor; a Charge Density Study

    DEFF Research Database (Denmark)

    Du, Jonathan J.; Hanrahan, Jane Rouse; Solomon, V. Raja

    2018-01-01

    Experimental charge density distribution studies, complemented by quantum mechanical theoretical calculations, of a host-guest system comprised of a macrocycle (1) and barbital (2) in a 1:1 ratio (3) have been carried out via high resolution single crystal X-ray diffraction. The data was modelled...... molecule. Visual comparison of the conformations of the macrocyclic ring shows the rotation by 180° of an amide bond attributed to competitive hydrogen bonding. It was found the intraannular and extraannular molecules inside were orientated to maximise the number of hydrogen bonds present...

  8. Use of a macrocyclic antibiotic as the chiral selector for enantiomeric separations by TLC

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, D.W.; Zhou, Y. (Univ. of Missouri, Rolla, MO (United States). Dept. of Chemistry)

    1994-01-01

    The macrocyclic antibiotic, vancomycin, was used as a chiral mobile phase additive for the thin layer chromatographic (TLC) resolution of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatized amino acids, racemic drugs and dansyl-amino acids. Excellent separations were achieved for most of these compounds in the reversed phase mode. Both the nature of the stationary phase and the composition of the mobile phase strongly influenced enantiomeric resolution. The best results were obtained using diphenyl stationary phases. Acetonitrile was the organic modifier that produced the most effective separations with the shortest development times. It is highly likely that macrocyclic antibiotics will play a major role in future enantiomeric separations.

  9. A toxicological and dermatological assessment of macrocyclic lactone and lactide derivatives when used as fragrance ingredients

    DEFF Research Database (Denmark)

    Belsito, D.; Bickers, D.; Bruze, M.

    2011-01-01

    The Macrocyclic Lactone and Lactide derivative (ML) group of fragrance ingredients was critically evaluated for safety following a complete literature search. For high end users, calculated maximum dermal exposures vary from 0.47% to 11.15%; systemic exposures vary from 0.0008 to 0.25 mg/kg/day. ......The Macrocyclic Lactone and Lactide derivative (ML) group of fragrance ingredients was critically evaluated for safety following a complete literature search. For high end users, calculated maximum dermal exposures vary from 0.47% to 11.15%; systemic exposures vary from 0.0008 to 0.25 mg...

  10. Complexation of imidazopyridine-based cations with a 24-crown-8 ether host: [2]pseudorotaxane and partially threaded structures.

    Science.gov (United States)

    Moreno-Olivares, Surisadai I; Cervantes, Ruy; Tiburcio, Jorge

    2013-11-01

    A new series of linear molecules derived from 1,2-bis(imidazopyridin-2-yl)ethane can fully or partially penetrate the cavity of the dibenzo-24-crown-8 macrocycle to produce a new family of host-guest complexes. Protonation or alkylation of the nitrogen atoms on the pyridine rings led to an increase in the guest total positive charge up to 4+ and simultaneously generated two new recognition sites (pyridinium motifs) that are in competition with the 1,2-bis(benzimidazole)ethane motif for the crown ether. The relative position of the pyridine ring and the chemical nature of the N-substituent determined the preferred motif and the host-guest complex geometry: (i) for linear guests with relatively bulky groups (i.e., a benzyl substituent), the 1,2-bis(benzimidazole)ethane motif is favored, leading to a fully threaded complex with a [2]pseudorotaxane geometry; (ii) for small substituents, such as -H and -CH3 groups, regardless of the guest shape, the pyridinium motifs are preferred, leading to external partially threaded complexes in a 2:1 host to guest stoichiometry.

  11. Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

    Science.gov (United States)

    Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

    2017-06-01

    A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

  12. The Porphobilinogen Conundrum in Prebiotic Routes to Tetrapyrrole Macrocycles

    Science.gov (United States)

    Taniguchi, Masahiko; Ptaszek, Marcin; Chandrashaker, Vanampally; Lindsey, Jonathan S.

    2017-03-01

    Attempts to develop a credible prebiotic route to tetrapyrroles have relied on enzyme-free recapitulation of the extant biosynthesis, but this process has foundered from the inability to form the pyrrole porphobilinogen ( PBG) in good yield by self-condensation of the precursor δ-aminolevulinic acid ( ALA). PBG undergoes robust oligomerization in aqueous solution to give uroporphyrinogen (4 isomers) in good yield. ALA, PBG, and uroporphyrinogen III are universal precursors to all known tetrapyrrole macrocycles. The enzymic formation of PBG entails carbon-carbon bond formation between the less stable enolate/enamine of one ALA molecule (3-position) and the carbonyl/imine (4-position) of the second ALA molecule; without enzymes, the first ALA reacts at the more stable enolate/enamine (5-position) and gives the pyrrole pseudo-PBG. pseudo-PBG cannot self-condense, yet has one open α-pyrrole position and is proposed to be a terminator of oligopyrromethane chain-growth from PBG. Here, 23 analogues of ALA have been subjected to density functional theoretical (DFT) calculations, but no motif has been identified that directs reaction at the 3-position. Deuteriation experiments suggested 5-(phosphonooxy)levulinic acid would react preferentially at the 3- versus 5-position, but a hybrid condensation with ALA gave no observable uroporphyrin. The results suggest efforts toward a biomimetic, enzyme-free route to tetrapyrroles from ALA should turn away from structure-directed reactions and focus on catalysts that orient the two aminoketones to form PBG in a kinetically controlled process, thereby avoiding formation of pseudo-PBG.

  13. Crown ether derivatives of EDTA: Pt. 6

    International Nuclear Information System (INIS)

    Liu Zhongqun; Qin Shengying; Chen Shaojin; Tan Lin

    1988-01-01

    EDTA-diaminodibenzo-18-crown-6 (cis- and trans-) condensation polymer is a new compound of crown ether derivatives of EDTA. In this paper the adsorption behaviors of U(IV) and U(VI) on this polymer from chloride solutions and effects of hydrochloric acid concentrations, salting-out agents and organic solvents on distribution coefficient (K d ) of uranium are investigated. Adsorption mechanism of uranyl ion (UO 2 2+ ) on this polymer was studied with IR spectra and by means of the adsorption behaviors of compounds of similar structure. Experimental results show that both polyether section and carboxyl groups in EDTA-diaminodibenzo-18-crown-6 take part in complexation with uranyl ion and synergistic effect appeared

  14. Crown ratio influences allometric scaling in trees

    Science.gov (United States)

    Annikki Makela; Harry T. Valentine

    2006-01-01

    Allometric theories suggest that the size and shape of organisms follow universal rules, with a tendency toward quarter-power scaling. In woody plants, however, structure is influenced by branch death and shedding, which leads to decreasing crown ratios, accumulation of heartwood, and stem and branch tapering. This paper examines the impacts on allometric scaling of...

  15. The molecular genetics of crown gall tumorigenesis

    International Nuclear Information System (INIS)

    Hooykaas, P.J.J.; Schilperoort, R.A.

    1984-01-01

    The phytopathogenic bacteria Agrobacterium tumefaciens and A. rhizogenes are the causative agents of the widespread plant diseases ''crown gall'' and ''hairy root'' respectively. It is now well established that virulent strains of these bacterial species transfer a piece of bacterial DNA into plant cells, thereby transforming these into tumor cells. In research much attention has been paid to the agrobacteria for several reasons. First is the desire to develop a system for the genetic engineering of plant cells based on the natural system for gene transfer between Agrobacterium species and plant cells. Second, there is a striking resemblance between the etiology of animal cancers and the plant cancer crown gall that was recognized as early as in 1927. This led to basic studies on the process of plant tumor induction and on the recovery of plant cells from the tumorous state. A third important interest lies in crown gall as a disease that is the cause of economically important losses in agriculture an horticulture in Europe, North America, and Austrailia. Research has been aimed at finding means to prevent crown gall and to cure plants of this disease

  16. Navigating through the Crown land process

    Energy Technology Data Exchange (ETDEWEB)

    Dawson, M. [Samsung Renewable Energy Inc., ON (Canada)

    2010-07-01

    Samsung Communications and Technology (Samsung C and T) and the Korea Electric Power Corporation are planning to invest approximately $7 billion to generate 2500 MW of wind and solar energy in Ontario. The plan was centred around the green energy investment agreement signed in January 2010. To date, only 1 project in Ontario has been permitted for development on Crown land, and there have been 3 different versions of the Crown land policy and procedure for the development of wind power projects. The Crown land process is challenged by issues related to grandfathering, timing, competing processes, and the Endangered Species Act. Guidance is needed to identify requirements for studies and evaluation processes. Additional studies are often required by government agencies when new documents and results are reviewed. Projects are also delayed when new species are added to the endangered species list. Wind power developers must keep abreast of proposed regulations and guidelines to ensure that work programs are not delayed. An overview of the current Crown land development process was included. tabs., figs.

  17. Paraphoma crown rot of pyrethrum (Tanacetum cinerariifolium)

    NARCIS (Netherlands)

    Moslemi, Azin; Ades, Peter Kevin; Groom, Tim; Crous, Pedro; Nicolas, Marc Edward; Taylor, Paul William James

    2016-01-01

    Pyrethrum (Tanacetum cinerariifolium) is commercially cultivated for the extraction of natural pyrethrin insecticides from the oil glands inside seeds. Yield-decline has caused significant yield losses in Tasmania during the last decade. A new pathogen of pyrethrum causing crown rot and reduced

  18. Rhizoctonia crown and root rot disease nursery

    Science.gov (United States)

    The BSDF cooperative CRR Eastern Evaluation Nursery Rhizoctonia crown and root rot Evaluation Nursery in 2016 was a randomized complete-block design with five replications in 15 feet long, one-row plots (20 in row spacing), at the Saginaw Valley Research and Education Center near Frankenmuth, MI. F...

  19. Total synthesis of complestatin: development of a Pd(0)-mediated indole annulation for macrocyclization.

    Science.gov (United States)

    Shimamura, Hiroyuki; Breazzano, Steven P; Garfunkle, Joie; Kimball, F Scott; Trzupek, John D; Boger, Dale L

    2010-06-09

    Full details of the initial development and continued examination of a powerful intramolecular palladium(0)-mediated indole annulation for macrocyclization closure of the strained 16-membered biaryl ring system found in complestatin (1, chloropeptin II) and the definition of factors impacting its intrinsic atropodiastereoselectivity are described. Its examination and use in an alternative, second-generation total synthesis of complestatin are detailed in which the order of the macrocyclization reactions was reversed from our first-generation total synthesis. In this approach and with the ABCD biaryl ether ring system in place, the key Larock cyclization was conducted with substrate 36 (containing four phenols, five secondary amides, one carbamate, and four labile aryl chlorides) and provided the product 37 (56%) exclusively as a single atropisomer (>20:1, detection limits) possessing the natural (R)-configuration. In this instance, the complexity of the substrate and the reverse macrocyclization order did not diminish the atropodiastereoselectivity; rather, it provided an improvement over the 4:1 selectivity that was observed with the analogous substrate used to provide the isolated DEF ring system in our first-generation approach. Just as significant, the atroposelectivity represents a complete reversal of the diasteroselectivity observed with analogous macrocyclizations conducted using a Suzuki biaryl coupling.

  20. Sceliphrolactam, a polyene macrocyclic lactam from a wasp-associated Streptomyces sp

    DEFF Research Database (Denmark)

    Oh, Dong-Chan; Poulsen, Michael; Currie, Cameron R

    2011-01-01

    A previously unreported 26-membered polyene macrocyclic lactam, sceliphrolactam, was isolated from an actinomycete, Streptomyces sp., associated with the mud dauber, Sceliphron caementarium. Sceliphrolactam's structure was determined by 1D- and 2D-NMR, MS, UV, and IR spectral analysis. Sceliphrol...

  1. Study of behaviour of Ni(III) macrocyclic complexes in acidic ...

    Indian Academy of Sciences (India)

    The Cu(II) ion-catalysed kinetics of oxidation of H2O2 by [NiIIIL] [where L ... The rate of the reaction of both complexes with hydrogen peroxide shows contrasting ... enhanced kinetic and thermodynamic stabilities. The redox chemistry of synthetic poly-aza macrocycles explores the properties of nickel containing enzymes.1.

  2. Reactions of copper macrocycles with antioxidants and HOCl: potential for biological redox sensing.

    Science.gov (United States)

    Sowden, Rebecca J; Trotter, Katherine D; Dunbar, Lynsey; Craig, Gemma; Erdemli, Omer; Spickett, Corinne M; Reglinski, John

    2013-02-01

    A series of simple copper N(2)S(2) macrocycles were examined for their potential as biological redox sensors, following previous characterization of their redox potentials and crystal structures. The divalent species were reduced by glutathione or ascorbate at a biologically relevant pH in aqueous buffer. A less efficient reduction was also achieved by vitamin E in DMSO. Oxidation of the corresponding univalent copper species by sodium hypochlorite resulted in only partial (~65 %) recovery of the divalent form. This was concluded to be due to competition between metal oxidation and ligand oxidation, which is believed to contribute to macrocycle demetallation. Electrospray mass spectrometry confirmed that ligand oxidation had occurred. Moreover, the macrocyclic complexes could be demetallated by incubation with EDTA and bovine serum albumin, demonstrating that they would be inappropriate for use in biological systems. The susceptibility to oxidation and demetallation was hypothesized to be due to oxidation of the secondary amines. Consequently these were modified to incorporate additional oxygen donor atoms. This modification led to greater resistance to demetallation and ligand oxidation, providing a better platform for further development of copper macrocycles as redox sensors for use in biological systems.

  3. Design and synthesis of macrocyclic peptidyl hydroxamates as peptide deformylase inhibitors.

    Science.gov (United States)

    Shen, Gang; Zhu, Jinge; Simpson, Anthony M; Pei, Dehua

    2008-05-15

    Macrocyclic peptidyl hydroxamates were designed, synthesized, and evaluated as peptide deformylase (PDF) inhibitors. The most potent compound exhibited tight, slow-binding inhibition of Escherichia coli PDF (K(I)(*)=4.4 nM) and had potent antibacterial activity against Gram-positive bacterium Bacillus subtilis (MIC=2-4 microg/mL).

  4. Synthesis and extended activity of triazole-containing macrocyclic protease inhibitors

    DEFF Research Database (Denmark)

    Pehere, A.D.; Pietsch, M.; Gütschow, M.

    2013-01-01

    of their activity against a panel of proteases. Acyclic azidoalkyne-based aldehydes are also evaluated for comparison. The macrocyclic peptidomimetics showed considerable activity towards calpain II, cathepsin L and S, and the 20S proteasome chymotrypsin-like activity. Some of the first examples of highly potent...

  5. Photoswitchable Dihydroazulene Macrocycles for Solar Energy Storage: The Effects of Ring Strain.

    Science.gov (United States)

    Vlasceanu, Alexandru; Frandsen, Benjamin N; Skov, Anders B; Hansen, Anne Schou; Rasmussen, Mads Georg; Kjaergaard, Henrik G; Mikkelsen, Kurt V; Nielsen, Mogens Brøndsted

    2017-10-06

    Efficient energy storage and release are two major challenges of solar energy harvesting technologies. The development of molecular solar thermal systems presents one approach to address these issues by tuning the isomerization reactions of photo/thermoswitches. Here we show that the incorporation of photoswitches into macrocyclic structures is a particularly attractive solution for increasing the storage time. We present the synthesis and properties of a series of macrocycles incorporating two dihydroazulene (DHA) photoswitching subunits, bridged by linkers of varying chain length. Independent of ring size, all macrocycles exhibit stepwise, light-induced, ring-opening reactions (DHA-DHA to DHA-VHF to VHF-VHF; VHF = vinylheptafulvene) with the first DHA undergoing isomerization with a similar efficiency as the uncyclized parent system while the second (DHA-VHF to VHF-VHF) is significantly slower. The energy-releasing, VHF-to-DHA, ring closures also occur in a stepwise manner and are systematically found to proceed slower in the more strained (smaller) cycles, but in all cases with a remarkably slow conversion of the second VHF to DHA. We managed to increase the half-life of the second VHF-to-DHA conversion from 65 to 202 h at room temperature by simply decreasing the ring size. A computational study reveals the smallest macrocycle to have the most energetic VHF-VHF state and hence highest energy density.

  6. Towards tumour targeting with copper-radiolabelled macrocycle-antibody conjugates

    Energy Technology Data Exchange (ETDEWEB)

    Morphy, J.R.; Parker, David; Kataky, Ritu; Harrison, Alice; Walker, Carole; Eaton, M.A.W.; Millican, Andrew; Phipps, Alison

    1989-06-15

    Tetraaza-macrocycles covalently attached to a monoclonal antibody may be efficiently radiolabelled with /sup 64/Cu or /sup 67/Cu at pH4, minimising non-specific binding to the protein, giving a kinetically stable conjugate in vivo. (author).

  7. Dimetal Complexes of a Bibrachial 2+2 Thiolate-based Macrocycle

    DEFF Research Database (Denmark)

    Lennartson, Anders; McKee, Vickie; Nelson, Jane

    2012-01-01

    Protocols for accessing the [2+3] and [2+2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)2, Mn(II)2, Ni(II)2 and Pd(II)2 complexes of the [2+2] bibrachial systems in which one arm of...

  8. Convergent Synthesis of Rigid Macrocycles Containing One and Two Tetrathiafulvalene Units

    DEFF Research Database (Denmark)

    Simonsen, Klaus B.; Thorup, Niels; Becher, Jan

    1997-01-01

    The synthesis of rigid tetrathiafulvalenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry...... and by X-ray crystallography....

  9. Macrocyclic Peptoid–Peptide Hybrids as Inhibitors of Class I Histone Deacetylases

    DEFF Research Database (Denmark)

    Olsen, Christian Adam; Montero, Ana; Leman, Luke J.

    2012-01-01

    We report the design, synthesis, and biological evaluation of the first macrocyclic peptoid-containing histone deacetylase (HDAC) inhibitors. The compounds selectively inhibit human class I HDAC isoforms in vitro, with no inhibition of the tubulin deacetylase activity associated with class IIb HDAC...

  10. Metacridamides A and B, bioactive macrocycles from conidia of the entomopathogenic fungus Metarhizium acridum

    Science.gov (United States)

    Metarhizium acridum, an entomopathogenic fungus, has been commercialized and used successfully for biocontrol of grasshopper pests in Africa and Australia. Its conidia produce two novel 17-membered macrocycles, metacridamides A (1) and B (2), which consist of a Phe unit condensed with a nonaketide....

  11. Experimental and DFT study on complexation of Eu3+ with a macrocyclic lactam receptor

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Vaňura, P.; Sedláková, Zdeňka

    2013-01-01

    Roč. 24, č. 6 (2013), s. 2149-2153 ISSN 1040-0400 Institutional support: RVO:61388955 ; RVO:61389013 Keywords : europium * macrocyclic lactam receptor * complexation Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 1.900, year: 2013

  12. Complexation of Eu3+ with a macrocyclic lactam receptor: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Záliš, Stanislav; Sedláková, Zdeňka; Vaňura, P.

    2013-01-01

    Roč. 1038, APR 2013 (2013), s. 216-219 ISSN 0022-2860 Institutional support: RVO:61388955 ; RVO:61389013 Keywords : europium * macrocyclic lactam receptor * complexation Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 1.599, year: 2013

  13. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  14. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  15. New atraumatic easy removal technique for permanently cemented crown

    Directory of Open Access Journals (Sweden)

    Pravinkumar G Patil

    2012-01-01

    Full Text Available Removal of a permanently cemented crown or fixed partial denture is a cumbersome procedure for a prosthodontist, especially when there is no purchase point available to remove it. The technique described in this article consists of sectioning of a crown on facial surface followed by removal of the crown with orthodontic plier. This technique does not damage the gingival/periodontal tissues or underlying tooth structure as the crown need not to be removed with jerky back-action force.

  16. m-Diethynylbenzene macrocycles: syntheses and self-association behavior in solution.

    Science.gov (United States)

    Tobe, Yoshito; Utsumi, Naoto; Kawabata, Kazuya; Nagano, Atsushi; Adachi, Kiyomi; Araki, Shunji; Sonoda, Motohiro; Hirose, Keiji; Naemura, Koichiro

    2002-05-15

    m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4(n)]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated. Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the (1)H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2(n)]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates pi-pi stacking interactions.

  17. A Focus on Triazolium as a Multipurpose Molecular Station for pH-Sensitive Interlocked Crown-Ether-Based Molecular Machines.

    Science.gov (United States)

    Coutrot, Frédéric

    2015-10-01

    The control of motion of one element with respect to others in an interlocked architecture allows for different co-conformational states of a molecule. This can result in variations of physical or chemical properties. The increase of knowledge in the field of molecular interactions led to the design, the synthesis, and the study of various systems of molecular machinery in a wide range of interlocked architectures. In this field, the discovery of new molecular stations for macrocycles is an attractive way to conceive original molecular machines. In the very recent past, the triazolium moiety proved to interact with crown ethers in interlocked molecules, so that it could be used as an ideal molecular station. It also served as a molecular barrier in order to lock interlaced structures or to compartmentalize interlocked molecular machines. This review describes the recently reported examples of pH-sensitive triazolium-containing molecular machines and their peculiar features.

  18. Digital photography for urban street tree crown conditions

    Science.gov (United States)

    Neil A. Clark; Sang-Mook Lee; William A. Bechtold; Gregory A. Reams

    2006-01-01

    Crown variables such as height, diameter, live crown ratio, dieback, transparency, and density are all collected as part of the overall crown assessment (USDA 2004). Transparency and density are related to the amount of foliage and thus the photosynthetic potential of the tree. These measurements are both currently based on visual estimates and have been shown to be...

  19. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Temporary crown and bridge resin. 872.3770 Section... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a) Identification. A temporary crown and bridge resin is a device composed of a material, such as...

  20. Evaluation of sampling strategies to estimate crown biomass

    Science.gov (United States)

    Krishna P Poudel; Hailemariam Temesgen; Andrew N Gray

    2015-01-01

    Depending on tree and site characteristics crown biomass accounts for a significant portion of the total aboveground biomass in the tree. Crown biomass estimation is useful for different purposes including evaluating the economic feasibility of crown utilization for energy production or forest products, fuel load assessments and fire management strategies, and wildfire...

  1. Fracture Resistance Force of Primary Molar Crowns Milled from ...

    African Journals Online (AJOL)

    2018-04-04

    Apr 4, 2018 ... molar stainless steel crown (SSC) and stored in water at 37°C for 30 days. The crowns were seated on Cr‑Co ... model) or chairside (in‑office system model) CAD/ ..... crowns, deformation may be observed instead of fracture.

  2. Fatigue resistance of CAD/CAM resin composite molar crowns.

    NARCIS (Netherlands)

    Shembish, F.A.; Tong, H.; Kaizer, M.; Janal, M.N.; Thompson, V.P.; Opdam, N.J.M.; Zhang, Y.

    2016-01-01

    OBJECTIVE: To demonstrate the fatigue behavior of CAD/CAM resin composite molar crowns using a mouth-motion step-stress fatigue test. Monolithic leucite-reinforced glass-ceramic crowns were used as a reference. METHODS: Fully anatomically shaped monolithic resin composite molar crowns (Lava

  3. MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold-Diverse Macrocyclic Libraries.

    Science.gov (United States)

    Saupe, Jörn; Kunz, Oliver; Haustedt, Lars Ole; Jakupovic, Sven; Mang, Christian

    2017-09-04

    Macrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide-based scaffolds is reported. The process, named here as "MacroEvoLution", is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  4. Synergistic extraction of some divalent metal cations into nitrobenzene by using strontium dicarbollylcobaltate and electroneutral macrocyclic lactam receptor

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Sedláková, Zdeňka; Vaňura, P.; Selucký, P.

    2013-01-01

    Roč. 295, č. 3 (2013), s. 2263-2266 ISSN 0236-5731 Institutional support: RVO:61389013 Keywords : divalent metal cations * macrocyclic lactam receptor * complexation Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.415, year: 2013

  5. Dentin-bonded all-ceramic crowns: current status.

    Science.gov (United States)

    Burke, F J; Qualtrough, A J; Hale, R W

    1998-04-01

    Dentin-bonded all-ceramic crowns employ contemporary techniques to lute the crown to the tooth using a resin luting material and dentin-bonding system. The advantages of these crowns are that they provide good esthetics and fracture resistance and can be used in cases of substantial tooth loss. Their principal disadvantages are that the luting procedure is more time-consuming and that these crowns should not be used where margins are subgingival. Dentin-bonded all-ceramic crowns may be a useful addition to the dentist's armamentarium, but long-term clinical studies are needed to fully assess their performance.

  6. Wavelength selection in the crown splash

    Science.gov (United States)

    Zhang, Li V.; Brunet, Philippe; Eggers, Jens; Deegan, Robert D.

    2010-12-01

    The impact of a drop onto a liquid layer produces a splash that results from the ejection and dissolution of one or more liquid sheets, which expand radially from the point of impact. In the crown splash parameter regime, secondary droplets appear at fairly regularly spaced intervals along the rim of the sheet. By performing many experiments for the same parameter values, we measure the spectrum of small-amplitude perturbations growing on the rim. We show that for a range of parameters in the crown splash regime, the generation of secondary droplets results from a Rayleigh-Plateau instability of the rim, whose shape is almost cylindrical. In our theoretical calculation, we include the time dependence of the base state. The remaining irregularity of the pattern is explained by the finite width of the Rayleigh-Plateau dispersion relation. Alternative mechanisms, such as the Rayleigh-Taylor instability, can be excluded for the experimental parameters of our study.

  7. Chemical Editing of Macrocyclic Natural Products and Kinetic Profiling Reveal Slow, Tight-Binding Histone Deacetylase Inhibitors with Picomolar Affinities

    DEFF Research Database (Denmark)

    Kitir, Betül; Maolanon, Alex R.; Ohm, Ragnhild G.

    2017-01-01

    medicines. Therefore, detailed mechanistic information and precise characterization of the chemical probes used to investigate the effects of HDAC enzymes are vital. We interrogated Nature's arsenal of macrocyclic nonribosomal peptide HDAC inhibitors by chemical synthesis and evaluation of more than 30...... natural products and analogues. This furnished surprising trends in binding affinities for the various macrocycles, which were then exploited for the design of highly potent class I and IIb HDAC inhibitors. Furthermore, thorough kinetic investigation revealed unexpected inhibitory mechanisms of important...

  8. Elliptic Fourier analysis of crown shapes in Quercus petraea trees

    Directory of Open Access Journals (Sweden)

    Ovidiu Hâruţa

    2011-02-01

    Full Text Available Shape is a fundamental morphological descriptor, significant in taxonomic research as well as in ecomorphology, one method of estimation being from digitally processed images. In the present study, were analysed shapes of Q. petraea crowns, pertaining to five different stem diameter classes, from three similar stands. Based on measurements on terrestrial digital vertical photos, crown size analysis was performed and correlations between crown and stem variables were tested. Linear regression equations between crown volumes and dbh, and crown volumes and stem volumes were derived, explaining more than half of data variability. Employment of elliptic Fourier analysis (EFA, a powerful analysis tool, permitted the extraction of the mean shape from crowns, characterized by high morphological variability. The extracted, most important, coefficients were used to reconstruct the average shape of the crowns, using Inverse Fourier Transform. A mean shape of the crown, corresponding to stand conditions in which competition is added as influential shaping factor, aside genetic program of the species, is described for each stem diameter class. Crown regions with highest shape variability, from the perspective of stage developmentof the trees, were determined. Accordingly, the main crown shape characteristics are: crown elongation, mass center, asymmetry with regard to the main axis, lateral regions symmetrical and asymmetrical variations.

  9. Elliptic Fourier analysis of crown shapes in Quercus petraea trees

    Directory of Open Access Journals (Sweden)

    Ovidiu Hâruţa

    2011-06-01

    Full Text Available Shape is a fundamental morphological descriptor, significant in taxonomic research as well as in ecomorphology, one method of estimation being from digitally processed images. In the present study, were analysed shapes of Q. petraea crowns, pertaining to five different stem diameter classes, from three similar stands. Based on measurements on terrestrial digital vertical photos, crown size analysis was performed and correlations between crown and stem variables were tested. Linear regression equations between crown volumes and dbh, and crown volumes and stem volumes were derived, explaining more than half of data variability. Employment of elliptic Fourier analysis (EFA, a powerful analysis tool, permitted the extraction of the mean shape from crowns, characterized by high morphological variability. The extracted, most important, coefficients were used to reconstruct the average shape of the crowns, using Inverse Fourier Transform. A mean shape of the crown, corresponding to stand conditions in which competition is added as influential shaping factor, aside genetic program of the species, is described for each stem diameter class. Crown regions with highest shape variability, from the perspective of stage development of the trees, were determined. Accordingly, the main crown shape characteristics are: crown elongation, centroid position, asymmetry with regard to the main axis, lateral regions symmetrical and asymmetrical variations. 

  10. Crown structure, radiation absorption, photosynthesis and transpiration

    OpenAIRE

    Wang, Yingping

    1988-01-01

    A complex simulation model, MAESTRO, has been developed and validated against field measurements in plantation in both Scotland and Australia. It has been shown that MAESTRO can reasonably predict the daily course of PAR (photosynetically active radiation) transmittance at points below the canopies of radiata pine and Sitka spruce plantations. 1. Four structural properties of the Sitka spruce tree crown have been identified and evaluation in relation to PAR absorption, photosynthesis and ...

  11. Solvent Effects on Cesium Complexation with Crown Ethers from Liquid to Supercritical Fluids

    International Nuclear Information System (INIS)

    Wai, Chien M.; Rustenholtz, Anne; Wang, Shaofen; Lee, Su-Chen; Herman, Jamie; Porter, Richard A.

    2004-01-01

    Nuclear magnetic resonance (NMR) techniques were used to study crown ether-water interactions in solvents of low dielectric constants such as chloroform and carbon tetrachloride. Water forms a 1:1 complex with a number of crown ethers including 12-crown-4, 15-crown-5, 18-crown-6, dicyclohexano-18=crown-6, dicyclohexano-24-crown 8, and dibenzl-24-crown-8 in chloroform. Among these crown ethers, the 18-crown-6-H2 complex has the largest equilibrium constant (K=545) and 97% of the crown is complexed to water in chloroform. Addition of carbon tetrachloride to chloroform lowers the equilibrium constants of the crown-water complexes. The partition coefficients of crown ethers (D=crown in water/crown in solvent) between water and organic solvent also vary with solvent composition

  12. Simple Syntheses of Two New Benzo-Fused Macrocycles Incorporating Chalcone Moiety.

    Science.gov (United States)

    Mondal, Rina; Samanta, Swati; Sarkar, Saheli; Mallik, Asok K

    2014-01-01

    Simple syntheses of the benzo-fused 26-membered macrocyclic bischalcone (19E,43E)-2.11.27.36-tetroxaheptacyclo[44.4.0.0(4,9).0(12,17).0(21,26).0(29,34).0(37,42)]pentaconta-1(46),4(9),5,7,12(17),13,15,19,21,23,25,29,31,33,37,39,41,43,47,49-icosaene-18,45-dione (3) and the benzo-fused 13-membered macrocyclic chalcone (19E)-2.11-dioxatetracyclo[19.4.0.0(4,9).0(12,17)]pentacosa-1(25),4(9),5,7,12(17),13,15,19,21,23-decaen-18-one (5) using very common starting materials and reagents are described. The compounds are new and they have been characterized from their analytical and spectral data.

  13. Synthetic approaches to aromatic belts: building up strain in macrocyclic polyarenes.

    Science.gov (United States)

    Eisenberg, David; Shenhar, Roy; Rabinovitz, Mordecai

    2010-08-01

    This tutorial review discusses synthetic strategies towards aromatic belts, defined here as double-stranded conjugated macrocycles, such as [n]cyclacenes, [n]cyclophenacenes, Schlüter belt, and Vögtle belt. Their appeal stems, firstly, from the unique nature of their conjugation, having p orbitals oriented radially rather than perpendicular to the plane of the macrocycle. Secondly, as aromatic belts are model compounds of carbon nanotubes of different chiralities, a synthetic strategy towards the buildup of structural strain in these compounds could finally open a route towards rational chemical synthesis of carbon nanotubes. The elusiveness of these compounds has stimulated fascinating and ingenious synthetic strategies over the last decades. The various strategies are classified here by their approach to the buildup of structural strain, which is the main obstacle in the preparation of these curved polyarenes.

  14. Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

    Directory of Open Access Journals (Sweden)

    Marco Caricato

    2012-06-01

    Full Text Available We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially chiral binol scaffolds, which incorporate either methoxy or acetoxy functionalities in the 2,2' positions and carboxylic functionalities in the external 3,3' positions, were used as the source of chirality. Two of these binaphthyls are joined through amidation reactions using rigid diaryl amines of differing shapes, to give homochiral tetraamidic macrocycles. The recognition properties of these supramolecular receptors have been analyzed, and the results indicate a modulation of binding affinities towards dicarboxylate anions, with a drastic change of binding mode depending on the steric and electronic features of the functional groups in the 2,2' positions.

  15. Ring strain and total syntheses of modified macrocycles of the isoplagiochin type

    Directory of Open Access Journals (Sweden)

    Andreas Speicher

    2009-12-01

    Full Text Available Macrocycles of the bisbibenzyl-type are natural products that are found exclusively in bryophytes (liverworts. The molecular framework of the subtype “isoplagiochin” is of substantial structural interest because of the chirality of the entire molecule, which arises from two biaryl axes in combination with two helical two-carbon units in a cyclic arrangement. From a structural as well as a synthetic point of view we report on the total synthesis of compounds which possess more rigid two-carbon biaryl bridges like stilbene (E or Z or even tolane moieties which were introduced starting with a Sonogashira protocol. The McMurry method proved to be a powerful tool for the cyclization to these considerably ring-strained macrocycles.

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

    KAUST Repository

    Ji, Xiaofan

    2018-02-13

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

  17. The influence of intraannular templates on the liquid crystallinity of shape-persistent macrocycles

    Directory of Open Access Journals (Sweden)

    Joscha Vollmeyer

    2014-04-01

    Full Text Available A series of shape-persistent phenylene–ethynylene–naphthylene–butadiynylene macrocycles with different extraannular alkyl groups and intraannular bridges is synthesized by oxidative Glaser-coupling of the appropriate precursors. The intraannular bridges serve in this case as templates that reduce the oligomerization even when the reaction is not performed under pseudo high-dilution conditions. The extraannular as well as the intraannular substituents have a strong influence on the thermal behavior of the compounds. With branched alkyl chains at the periphery, the macrocycles exhibit liquid crystalline (lc phases when the interior is empty or when the length of the alkyl bridge is just right to cross the ring. With a longer alkyl or an oligoethylene oxide bridge no lc phase is observed, most probably because the mesogene is no longer planar.

  18. Macrocyclic lactones: A versatile source for omega radiohalogenated fatty acid analogs

    International Nuclear Information System (INIS)

    Dougan, A.H.; Lyster, D.M.; Robertson, K.A.; Vincent, J.S.

    1984-01-01

    For each omega halogenated fatty acid there exists a potential omega hydroxy fatty acid and the corresponding macrocyclic lactone. The authors have utilized such lactones as starting materials for omega /sup 123/I fatty acid analogs intended for myocardial imaging. Macrocyclic musk lactones are industrially available; 120 analogs are described in the literature. The preparation requires saponification, tosylation, and radio-iodide substitution. Iodo-fatty acids are readily separated from tosylate fatty acids on TLC. While providing a secure source of 16-iodo-hexadecanoic acid and 17-iodo-heptadecanoic acid, the scheme allows ready access to a large number of untried fatty acid analogs. Examples presented are 16-iodo-hexadecanoic acid, 16-iodo-7-hexadecanoic acid, 16-iodo-12-oxa-hexadecanoic acid, 15-iodo-pentadecanoic acid, and 15-iodo-12-keto-pentadecanoic acid. Metabolic studies are in progress in mice and dogs to assess the utility of these analogs for myocardial imaging

  19. Lead Diversification through a Prins-Driven Macrocyclization Strategy: Application to C13-Diversified Bryostatin Analogues.

    Science.gov (United States)

    Wender, Paul A; Billingsley, Kelvin L

    2013-01-01

    The design, synthesis, and biological evaluation of a novel class of C13-diversified bryostatin analogues are described. An innovative and general strategy based on a Prins macrocyclization-nucleophilic trapping cascade was used to achieve late-stage diversification. In vitro analysis of selected library members revealed that modification at the C13 position of the bryostatin scaffold can be used as a diversification handle to regulate biological activity.

  20. A method for the preparation of lipophilic macrocyclic technetium-99m complexes

    International Nuclear Information System (INIS)

    Troutner, D.E.; Volkert, W.A.

    1991-01-01

    A procedure for the preparation of technetium complexes applicable as diagnostic radiopharmaceuticals is suggested and documented with 27 examples. Technetium-99m is reacted with a suitable complexant selected from the class of alkylenamine oximes containing 2 or 3 carbon atoms in the alkylene group. The lipophilic macrocyclic complexes possess an amine, amide, carboxy, carboxy ester, hydroxy or alkoxy group or a suitable electron acceptor group. (M.D.). 7 tabs

  1. Total synthesis of haterumalides NA and NC via a chromium-mediated macrocyclization.

    Science.gov (United States)

    Schomaker, Jennifer M; Borhan, Babak

    2008-09-17

    The syntheses of haterumalides NA and NC were accomplished via the macrocyclization of a chlorovinylidene chromium carbenoid onto a pendant aldehyde to generate the C8-C9 bond with the desired stereoisomer as the major product. Utilizing the latter chemistry enables access to both C9 hydroxylated (haterumalides NC and ND) and C9 deoxygenated forms (haterumalides NA, NB, and NE; via deoxygenation of the C9-hydroxyl).

  2. Synthesis and characterization of two new tetrapyrazolic macrocycles for the selective extraction of cesium cation

    Czech Academy of Sciences Publication Activity Database

    Harit, T.; Malek, F.; El Bali, B.; Dušek, Michal; Kučeráková, Monika

    2016-01-01

    Roč. 72, č. 27-28 (2016), s. 3966-3973 ISSN 0040-4020 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : cesium cation * liquid–liquid extraction * macrocycle * pyrazole * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.651, year: 2016

  3. Recognition of thymine in DNA bulges by a Zn(II) macrocyclic complex.

    Science.gov (United States)

    del Mundo, Imee Marie A; Fountain, Matthew A; Morrow, Janet R

    2011-08-14

    A Zn(II) macrocyclic complex with appended quinoline is a bifunctional recognition agent that uses both the Zn(II) center and the pendent aromatic group to bind to thymine in bulges with good selectivity over DNA containing G, C or A bulges. Spectroscopic studies show that the stem containing the bulge stays largely intact in a DNA hairpin with the Zn(II) complex bound to the thymine bulge. This journal is © The Royal Society of Chemistry 2011

  4. On-Surface Pseudo-High-Dilution Synthesis of Macrocycles: Principle and Mechanism.

    Science.gov (United States)

    Fan, Qitang; Wang, Tao; Dai, Jingya; Kuttner, Julian; Hilt, Gerhard; Gottfried, J Michael; Zhu, Junfa

    2017-05-23

    Macrocycles have attracted much attention due to their specific "endless" topology, which results in extraordinary properties compared to related linear (open-chain) molecules. However, challenges still remain in their controlled synthesis with well-defined constitution and geometry. Here, we report the successful application of the (pseudo-)high-dilution method to the conditions of on-surface synthesis in ultrahigh vacuum. This approach leads to high yields (up to 84%) of cyclic hyperbenzene ([18]-honeycombene) via an Ullmann-type reaction from 4,4″-dibromo-meta-terphenyl (DMTP) as precursor on a Ag(111) surface. The mechanism of macrocycle formation was explored in detail using scanning tunneling microscopy and X-ray photoemission spectroscopy. We propose that the dominant pathway for hyperbenzene (MTP) 6 formation is the stepwise desilverization of an organometallic (MTP-Ag) 6 macrocycle, which forms via cyclization of (MTP-Ag) 6 chains under pseudo-high-dilution conditions. The high probability of cyclization on the stage of the organometallic phase results from the reversibility of the C-Ag bond. The case is different from that in solution, in which cyclization typically occurs on the stage of a covalently bonded open-chain precursor. This difference in the cyclization mechanism on a surface compared to that in solution stems mainly from the 2D confinement exerted by the surface template, which hinders the flipping of chain segments necessary for cyclization.

  5. Design and synthesis of macrocyclic ligands and their complexes of lanthanides and actinides

    International Nuclear Information System (INIS)

    Alexander, V.

    1995-01-01

    A review article which covers the various design and synthetic strategies developed to synthesize macrocyclic complexes of lanthanides and actinides, their structural features, quantitative studies on the stabilities of these complexes, their applications, and the structure-reactivity principle would be an asset for those who are actively engaged in this area of research. This review is also purported to give a comprehensive view of the current status of this area of research to the beginners and to highlight the application of this chemical research to emerging nonchemical applications to lure the potential workers. The coordination template effect provides a general strategy for the synthesis of a wide variety of discrete metal complexes. The principal conceptual and experimental development that have established and exploited this strategy are briefly outlined. A brief review of the coordination template effect and subsequent developments in the design of macrocyclic complexes of alkali, alkaline earth, and transition metal ions is presented as an essential basis for the rational design of new macrocyclic complexes of lanthanides and actinides. The exciting aspect of this chemistry is that in the majority of cases the molecules meet the design criteria very well. It is evident that in an increasing number of cases the driving force behind the synthetic effort is the desire to create a molecule which will enable the user to make specific applications. 506 refs

  6. Hydrolyzable tannins of tamaricaceous plants. III. Hellinoyl- and macrocyclic-type ellagitannins from Tamarix nilotica.

    Science.gov (United States)

    Orabi, Mohamed A A; Taniguchi, Shoko; Yoshimura, Morio; Yoshida, Takashi; Kishino, Kaori; Sakagami, Hiroshi; Hatano, Tsutomu

    2010-05-28

    Three new hellinoyl-type ellagitannins, nilotinins M4 (7), D7 (8), and D8 (9), and a new macrocyclic-type, nilotinin D9 (10), together with eight known tannins, hirtellins B (2), C (11), and F (12), isohirtellin C (13), tamarixinin A (3), tellimagrandins I and II, and 1,2,6-tri-O-galloyl-beta-d-glucose (14), were isolated from an aqueous acetone extract of Tamarix nilotica dried leaves. Nilotinin M4 (7) is a monomeric tannin possessing a hellinoyl moiety. The structure of 8 demonstrated replacement of one of the HHDP groups at the glucose core O-4/O-6 in ordinary dimeric tannins with a galloyl moiety at O-6. This is a new structural feature among the tamaricaceous ellagitannins. On the basis of the results, reported spectroscopic assignments for 2, 3, and the macrocyclic tannins 11-13 were revised. Unusual shifts in the NMR spectra of these macrocyclic tannins are also discussed in relation to their conformations. Several tannins isolated from T. nilotica were assessed for possible cytotoxic activity against four human tumor cell lines, and nilotinin D8 (9) and hirtellin A (1) showed high cytotoxic effects.

  7. Synthesis of several tetraaza macrocyclic amine ligands and the biodistribution of their Tc-complexes

    International Nuclear Information System (INIS)

    Ketring, A.R.

    1982-01-01

    Several macrocyclic tetraaza ligands were synthesized and their /sup 99m/Tc-complexes prepared. The biological distribution of these complexes was examined to determine their possible utility as radiodiagnostic agents. The simplest of the macrocyclic tetraaza ligands studied, cyclam, forms a very stable cationic complex with Tc when pertechnetate is reduced with stannous ion in an aqueous solution of the ligand. When injected intravenously into mice Tc-cyclam was excreted predominantly by the urinary system. Derivatives of cyclam which were synthesized contained aromatic or aliphatic substituents and formed more lipophilic complexes with Tc. The complexes were formed in high yield as determined by paper chromatography, thin layer chromatography, electrophoresis and/or high performance liquid chromatography. Relative lipophilicities were determined for the complexes by octanol-to-water extractions. Animal studies using mice indicated there was an inverse relationship between the octanol-to-water extraction ratio and urinary excretion. Two of the complexes having relatively high octanol-to-water extraction ratios were significantly excreted by the hepatobiliary system with localization in the gall bladder. The complex having the highest octanol-to-water ratio was not excreted significantly by the hepatobiliary system, but cleared very slowly from the blood and localized in the liver, lungs, spleen and to some extent the heart. Derivatization of cyclam can be performed without greatly reducing its ability to complex Tc but greatly influencing the biological distribution of its Tc complex. This indicates that there is a potential for preparing radiodiagnostic agents using macrocyclic tetraaza ligands

  8. Macrocycle peptides delineate locked-open inhibition mechanism for microorganism phosphoglycerate mutases

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Hao; Dranchak, Patricia; Li, Zhiru; MacArthur, Ryan; Munson, Matthew S.; Mehzabeen, Nurjahan; Baird, Nathan J.; Battalie, Kevin P.; Ross, David; Lovell, Scott; Carlow, Clotilde K.S.; Suga, Hiroaki; Inglese, James (U of Tokyo); (NEB); (Kansas); (NIH); (NIST); (HHMI)

    2017-04-03

    Glycolytic interconversion of phosphoglycerate isomers is catalysed in numerous pathogenic microorganisms by a cofactor-independent mutase (iPGM) structurally distinct from the mammalian cofactor-dependent (dPGM) isozyme. The iPGM active site dynamically assembles through substrate-triggered movement of phosphatase and transferase domains creating a solvent inaccessible cavity. Here we identify alternate ligand binding regions using nematode iPGM to select and enrich lariat-like ligands from an mRNA-display macrocyclic peptide library containing >1012 members. Functional analysis of the ligands, named ipglycermides, demonstrates sub-nanomolar inhibition of iPGM with complete selectivity over dPGM. The crystal structure of an iPGM macrocyclic peptide complex illuminated an allosteric, locked-open inhibition mechanism placing the cyclic peptide at the bi-domain interface. This binding mode aligns the pendant lariat cysteine thiolate for coordination with the iPGM transition metal ion cluster. The extended charged, hydrophilic binding surface interaction rationalizes the persistent challenges these enzymes have presented to small-molecule screening efforts highlighting the important roles of macrocyclic peptides in expanding chemical diversity for ligand discovery.

  9. Chemical and Biological Significance of Oenothein B and Related Ellagitannin Oligomers with Macrocyclic Structure

    Directory of Open Access Journals (Sweden)

    Takashi Yoshida

    2018-03-01

    Full Text Available In 1990, Okuda et al. reported the first isolation and characterization of oenothein B, a unique ellagitannin dimer with a macrocyclic structure, from the Oenothera erythrosepala leaves. Since then, a variety of macrocyclic analogs, including trimeric–heptameric oligomers have been isolated from various medicinal plants belonging to Onagraceae, Lythraceae, and Myrtaceae. Among notable in vitro and in vivo biological activities reported for oenothein B are antioxidant, anti-inflammatory, enzyme inhibitory, antitumor, antimicrobial, and immunomodulatory activities. Oenothein B and related oligomers, and/or plant extracts containing them have thus attracted increasing interest as promising targets for the development of chemopreventive agents of life-related diseases associated with oxygen stress in human health. In order to better understand the significance of this type of ellagitannin in medicinal plants, this review summarizes (1 the structural characteristics of oenothein B and related dimers; (2 the oxidative metabolites of oenothein B up to heptameric oligomers; (3 the distribution of oenotheins and other macrocyclic analogs in the plant kingdom; and (4 the pharmacological activities hitherto documented for oenothein B, including those recently found by our laboratory.

  10. [Comparison of the clinical effects of selective laser melting deposition basal crowns and cobalt chromium alloy base crowns].

    Science.gov (United States)

    Li, Jing-min; Wang, Wei-qian; Ma, Jing-yuan

    2014-06-01

    To evaluate the clinical effects of selective laser melting (SLM) deposition basal crowns and cobalt chromium alloy casting base crowns. One hundred and sixty eight patients treated with either SLM deposition basal crowns (110 teeth) or cobalt chromium alloy casting basal crowns (110 teeth) were followed-up for 1 month, 6 months, 12 months and 24 months. The revised standard of American Public Health Association was used to evaluate the clinical effect of restoration, including the color of porcelain crowns, gingival inflammation, gingival margin discoloration, and crack or fracture. Data analysis was conducted with SPSS 20 software package for Student's t test and Chi-square test. Six cases were lost to follow-up. The patients who were treated with SLM deposition basal crowns (104 teeth) and cobalt chromium alloy casting base crowns (101 teeth) completed the study. Patients were more satisfied with SLM deposition cobalt chromium alloy porcelain crowns. There was 1 prosthesis with poor marginal fit after 24 months of restoration in SLM crowns. There were 6 prostheses with edge coloring and 8 with poor marginal fit in cobalt chromium alloy casting base crowns, which was significantly different between the 2 groups(P<0.05). The SLM deposition copings results in smaller edge coloring and better marginal fit than those of cobalt-chrome copings. Patients are pleased with short-term clinical results.

  11. Basal ganglia - thalamus and the crowning enigma

    Directory of Open Access Journals (Sweden)

    Marianela eGarcia-Munoz

    2015-11-01

    Full Text Available When Hubel (1982 referred to layer 1 of primary visual cortex as …a ‘crowning mystery’ to keep area-17 physiologists busy for years to come... he could have been talking about any cortical area. In the 80’s and 90’s there were no methods to examine this neuropile on the surface of the cortex: a tangled web of axons and dendrites from a variety of different places with unknown specificities and doubtful connections to the cortical output neurons some hundreds of microns below. Recently, three changes have made the crowning enigma less of an impossible mission: the clear presence of neurons in layer 1 (L1, the active conduction of voltage along apical dendrites and optogenetic methods that might allow us to look at one source of input at a time. For all of those reasons alone, it seems it is time to take seriously the function of L1. The functional properties of this layer will need to wait for more experiments but already L1 cells are GAD67 positive, i.e., inhibitory! They could reverse the sign of the thalamic glutamate (GLU input for the entire cortex. It is at least possible that in the near future normal activity of individual sources of L1 could be detected using genetic tools. We are at the outset of important times in the exploration of thalamic functions and perhaps the solution to the crowning enigma is within sight. Our review looks forward to that solution from the solid basis of the anatomy of the basal ganglia output to motor thalamus. We will focus on L1, its afferents, intrinsic neurons and its influence on responses of pyramidal neurons in layers 2/3 and 5. Since L1 is present in the whole cortex we will provide a general overview considering evidence mainly from the somatosensory cortex before focusing on motor cortex.

  12. Crown and bridge cements: clinical applications.

    Science.gov (United States)

    Bunek, Sabiha S; Powers, John M

    2012-12-01

    Cement selection can be confusing because factors such as substrate, the type of restoration, and patient needs must be considered. Some substrates require additional treatment before cementation. This article describes the most commonly used traditional crown and bridge cements (GI and RMGI) used for metal and metal-ceramic restorations, and resin cements used for all-ceramic restorations. Advantages, disadvantages, indications, and contraindications of cements have been reviewed. Recommended uses of cements for metal, ceramic, and laboratory composite restorations have been presented. General guidelines for surface treatment ot silica- and zirconia-based restorations when using resin cements have been discussed.

  13. Gamma-radiolysis of benzosubstituted crown ethers

    International Nuclear Information System (INIS)

    Grigor'ev, E.I.; Nesterov, S.V.; Mikhalitsyna, O.V.; Trakhtenberg, L.I.; Myasoedova, T.G.

    1992-01-01

    The products of gamma-radiolysis of benzosubstituted crown ethers, which are distiguished by the size of polyether ring, and alkylsubstituted DB18C6 are studied by the methods of ESR and mass-spectrometry. A mechanism of the radiolysis of the radiolysis of the studied compounds in the solid phase is proposed. It is shown that the prinicple radiolysis process is the rupture of C-O bond resulting in the stabilization of H atoms from group -CH 2 - of polyether ring is realized with a lower probability

  14. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  15. Elliptic Fourier analysis of crown shapes in Quercus petraea trees

    OpenAIRE

    Ovidiu Hâruţa

    2011-01-01

    Shape is a fundamental morphological descriptor, significant in taxonomic research as well as in ecomorphology, one method of estimation being from digitally processed images. In the present study, were analysed shapes of Q. petraea crowns, pertaining to five different stem diameter classes, from three similar stands. Based on measurements on terrestrial digital vertical photos, crown size analysis was performed and correlations between crown and stem variables were tested. Linear regression ...

  16. A Macrocyclic Peptide that Serves as a Cocrystallization Ligand and Inhibits the Function of a MATE Family Transporter

    Directory of Open Access Journals (Sweden)

    Hiroaki Suga

    2013-08-01

    Full Text Available The random non-standard peptide integrated discovery (RaPID system has proven to be a powerful approach to discover de novo natural product-like macrocyclic peptides that inhibit protein functions. We have recently reported three macrocyclic peptides that bind to Pyrococcus furiosus multidrug and toxic compound extrusion (PfMATE transporter and inhibit the transport function. Moreover, these macrocyclic peptides were successfully employed as cocrystallization ligands of selenomethionine-labeled PfMATE. In this report, we disclose the details of the RaPID selection strategy that led to the identification of these three macrocyclic peptides as well as a fourth macrocyclic peptide, MaD8, which is exclusively discussed in this article. MaD8 was found to bind within the cleft of PfMATE’s extracellular side and blocked the path of organic small molecules being extruded. The results of an ethidium bromide efflux assay confirmed the efflux inhibitory activity of MaD8, whose behavior was similar to that of previously reported MaD5.

  17. Descriptive statistics of tree crown condition in the North Central United States

    Science.gov (United States)

    KaDonna C. Randolph; Randall S. Morin; Jim Steinman

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Illinois, Indiana, Michigan, Minnesota, Missouri, and Wisconsin...

  18. Descriptive statistics of tree crown condition in the United States Interior West

    Science.gov (United States)

    KaDonna C. Randolph; Mike T. Thompson

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Colorado, Idaho, Nevada, Utah, and Wyoming between 1996 and...

  19. Descriptive statistics of tree crown condition in the Northeastern United States

    Science.gov (United States)

    KaDonna C. Randolph; Randall S. Morin; Jim Steinman

    2010-01-01

    The U.S. Forest Service Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes four crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in Connecticut, Delaware, Maine, Maryland, Massachusetts, New...

  20. Peptide Macrocycles Featuring a Backbone Secondary Amine: A Convenient Strategy for the Synthesis of Lipidated Cyclic and Bicyclic Peptides on Solid Support

    DEFF Research Database (Denmark)

    Oddo, Alberto; Münzker, Lena; Hansen, Paul Robert

    2015-01-01

    A convenient strategy for the on-resin synthesis of macrocyclic peptides (3- to 13-mers) via intramolecular halide substitution by a diamino acid is described. The method is compatible with standard Fmoc/tBu SPPS and affords a tail-to-side-chain macrocyclic peptide featuring an endocyclic secondary...

  1. Use of tetraaza-macrocycles for complexation of actinides in aqueous solutions. Validation of the process for the treatment of waste waters

    International Nuclear Information System (INIS)

    Chollet, Herve

    1994-01-01

    This report makes one's contribution to the study of the reactivity of free or fixed tetraaza-macrocycles. The major interest of this work concerns the following key-points: - Synthesis, spectral characterization and X-ray diffraction study of tetraaza-macrocycles N-tetra-functionalized, - Synthesis, physicochemical, chemicals and X-ray studies of macrocyclic complex in lanthanides and actinides series, - Synthesis and characterization of tetraaza-macrocycles grafted on organic and inorganic polymers, - Reactivity of macrocyclic ligands grafted on Merrifield's resin or silica gel in cerium, europium, uranium, plutonium and americium series, - Extraction of heavy metals in a solid-liquid process and measurements of a pilot. (author) [fr

  2. Automatic crown cover mapping to improve forest inventory

    Science.gov (United States)

    Claude Vidal; Jean-Guy Boureau; Nicolas Robert; Nicolas Py; Josiane Zerubia; Xavier Descombes; Guillaume Perrin

    2009-01-01

    To automatically analyze near infrared aerial photographs, the French National Institute for Research in Computer Science and Control developed together with the French National Forest Inventory (NFI) a method for automatic crown cover mapping. This method uses a Reverse Jump Monte Carlo Markov Chain algorithm to locate the crowns and describe those using ellipses or...

  3. Re/crowning the Jowo Śākyamuni

    DEFF Research Database (Denmark)

    Warner, Cameron

    2011-01-01

    of ritual observance and visions received.  In 1409, Tsongkhapa Lozang Drakpa  (1357-1419) crowned the Jowo, changing his doctrinal and iconographic representations.  I connect the controversy surrounding Tsongkhapa's decision to re/crown the Jowo in 1409 to the significance placed on authenticity...

  4. Usurpation of a Crowned Lapwing Vanellus coronatus nest by ...

    African Journals Online (AJOL)

    I report an instance of usurpation of a Crowned Lapwing Vanellus coronatus nest by a pair of African Wattled Lapwings Vanellus senegalensis. The nest, which originally contained a single Crowned Lapwing egg, eventually contained an additional three Wattled Lapwing eggs, before it was predated. Although parents of ...

  5. Incorporating crown dimensions into stem height and basal area for ...

    African Journals Online (AJOL)

    These increment models, with and without crown dimension were fitted to a modelling data set and the statistical significance of each of the crown dimensions was examined. All the models were then compared for predictive ability using an independent validation data set. The results obtained were similar for both the total ...

  6. Spectrophotometric evaluation of crown fragment a year after ...

    African Journals Online (AJOL)

    Background: Crown fracture is the most common type of fracture and frequently affects the anterior teeth. Crown fractures have been treated in several ways depending on the location and kind of fracture. This case emphasizes reattachment of fractured fragments using fiber-reinforced post. Also this case report underlines ...

  7. 18-Crown-6-polyether complexing with iodine

    International Nuclear Information System (INIS)

    Borovikov, Yu.Ya.

    1988-01-01

    Using the methods of dielectrometry, conductometry, calorimetry, UV, NMR and IR spectroscopy, 18-Crown-6-polyether complexing with iodine in chlorobenzene, benzotrifluoride, 1,2 dichloroethane is investigated. At the first stage external complexes (1) of the composition 1:1 (dipole momentum μ=7 D) is formed, which gradually regroups into internal complex (2) of the compositon 4:1. The time of 1 transition into 2 is inversely proportional to dielectric permeability of the medium. Enthalpy of 1 formation is close to 8.3 kcal/mol, which is 2,5 times higher than in cyclohexane solutions. Complex 1 is molecular, 2 is salt-like. Formation enthalpy of complex 2 of the components is not high, in dichlaroethane it is centrally symmetric and nonpolar, in chlorobenzene and benzotrifluoride-highly polar. In solid phase complex of the composition 1:2 is formed

  8. 18-Crown-6-polyether complexing with iodine

    Energy Technology Data Exchange (ETDEWEB)

    Borovikov, Yu Ya [AN Ukrainskoj SSR, Kiev (Ukrainian SSR). Inst. Organicheskoj Khimii

    1988-01-01

    Using the methods of dielectrometry, conductometry, calorimetry, UV, NMR and IR spectroscopy, 18-Crown-6-polyether complexing with iodine in chlorobenzene, benzotrifluoride, 1,2 dichloroethane is investigated. At the first stage external complexes (1) of the composition 1:1 (dipole momentum {mu}=7 D) is formed, which gradually regroups into internal complex (2) of the compositon 4:1. The time of 1 transition into 2 is inversely proportional to dielectric permeability of the medium. Enthalpy of 1 formation is close to 8.3 kcal/mol, which is 2,5 times higher than in cyclohexane solutions. Complex 1 is molecular, 2 is salt-like. Formation enthalpy of complex 2 of the components is not high, in dichlaroethane it is centrally symmetric and nonpolar, in chlorobenzene and benzotrifluoride-highly polar. In solid phase complex of the composition 1:2 is formed.

  9. Gingival pigmentation beneath a metallic crown

    International Nuclear Information System (INIS)

    Sakai, T.; Hirayasu, R.; Sakai, H.; Hashimoto, N.

    1988-01-01

    Light and electron microscopic studies and energy dispersive X-ray analysis disclosed that the essential cause of gingival discoloration following the placement of a metallic crown, was marked deposition of melanin pigment. Deposition of melanin pigment was observed in epithelial cells, on basement membranes, and in fibroblasts, macrophages and among intercellular ground substance of the proprial layer. Brown or dark brown colored granules were observed in the deep portion of the proprial layer. Some metallic elements as silver and sulfur were detected. It was presumed that these materials were dental metals accidentally implanted in gingival tissues during the therapeutic procedure. The deposition of melanin pigment closely corresponded with mucosal tissue where these materials were present in the deep portion of the proprial layer. These findings suggested that these materials influenced the physiological metabolism of melanin and induced its pathological deposition in the proprial tissue. (author)

  10. Calorimetric study of binding of some disaccharides with crown ethers

    Energy Technology Data Exchange (ETDEWEB)

    Davydova, Olga I.; Lebedeva, Nataliya Sh.; Parfenyuk, Elena V

    2004-11-01

    Isothermal titration calorimetry has been applied to the determination of the thermodynamic parameters of binding of {beta}-lactose, {alpha},{alpha}-trehalose and sucrose with 15-crown-5 and 18-crown-6 in water at 298.15 K. The formation of 1:1 molecular associates has been found for the systems studied except 18-crown-6 and {beta}-lactose. The associates are preferentially or completely entropy stabilized. The most stable associate is formed between {alpha},{alpha}-trehalose and 18-crown-6. The obtained values of thermodynamic parameters of binding are discussed from the point of view of solute-solvent interactions as well as conformational and structural peculiarities of the disaccharides (DS) and crown ethers (CE)

  11. Calorimetric study of binding of some disaccharides with crown ethers

    International Nuclear Information System (INIS)

    Davydova, Olga I.; Lebedeva, Nataliya Sh.; Parfenyuk, Elena V.

    2004-01-01

    Isothermal titration calorimetry has been applied to the determination of the thermodynamic parameters of binding of β-lactose, α,α-trehalose and sucrose with 15-crown-5 and 18-crown-6 in water at 298.15 K. The formation of 1:1 molecular associates has been found for the systems studied except 18-crown-6 and β-lactose. The associates are preferentially or completely entropy stabilized. The most stable associate is formed between α,α-trehalose and 18-crown-6. The obtained values of thermodynamic parameters of binding are discussed from the point of view of solute-solvent interactions as well as conformational and structural peculiarities of the disaccharides (DS) and crown ethers (CE)

  12. [Fractographic analysis of clinically failed anterior all ceramic crowns].

    Science.gov (United States)

    DU, Qian; Zhou, Min-bo; Zhang, Xin-ping; Zhao, Ke

    2012-04-01

    To identify the site of crack initiation and propagation path of clinically failed all ceramic crowns by fractographic analysis. Three clinically failed anterior IPS Empress II crowns and two anterior In-Ceram alumina crowns were retrieved. Fracture surfaces were examined using both optical stereo and scanning electron microscopy. Fractographic theory and fracture mechanics principles were applied to disclose the damage characteristics and fracture mode. All the crowns failed by cohesive failure within the veneer on the labial surface. Critical crack originated at the incisal contact area and propagated gingivally. Porosity was found within the veneer because of slurry preparation and the sintering of veneer powder. Cohesive failure within the veneer is the main failure mode of all ceramic crown. Veneer becomes vulnerable when flaws are present. To reduce the chances of chipping, multi-point occlusal contacts are recommended, and layering and sintering technique of veneering layer should also be improved.

  13. IPS Empress crown system: three-year clinical trial results.

    Science.gov (United States)

    Sorensen, J A; Choi, C; Fanuscu, M I; Mito, W T

    1998-02-01

    The IPS Empress system is a highly esthetic hot pressed glass ceramic material for fabrication of single crowns. Adhesive cementation of the system not only contributes to the esthetics but is necessary for increased strength of the crown. The purpose of this prospective clinical trials was to evaluate the longevity of 75 adhesively cemented Empress full crowns. An additional aim was to assess the adhesive cementation methodology and potential side effects. At the three-year point, one molar crown fractured for a 1.3 percent failure rate. The resin cementation technique that was employed exhibited a low incidence of microleakage with few clinical side effects. There was a 5.6 percent incidence of post-cementation sensitivity, with all symptoms subsiding by eight weeks. None of the crowns in the study required endodontic therapy.

  14. Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Mohammadipanah, Fatemeh; Hamedi, Javad [Department of Microbial Biotechnology, School of Biology and Center of Excellence in Phylogeny of Living Organisms, College of Science, University of Tehran, Tehran 14155-6455 (Iran, Islamic Republic of); University of Tehran Biocompound Collection (UTBC), Microbial Technology and Products Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Tahermansouri, Hasan [Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol (Iran, Islamic Republic of); Amini, Mostafa M. [Department of Chemistry, Shahid Behshti University, 1983963113, Tehran (Iran, Islamic Republic of)

    2015-06-30

    Graphical abstract: In an antibacterial test, grafted copper(II) macrocyclic complex on the surface of MWCNT showed higher antibacterial activity against Bacillus subtilis compared to the individual MWCNT-COOH and the complex. - Highlights: • Copper(II) tetraaza macrocyclic complex covalently bonded to modified MWCNT. • Grafting of the complex carried out via an interaction between −C(=O)Cl group and NH of the ligand. • The samples were subjected in an antibacterial assessment to compare their activity. • Immobilized complex showed higher antibacterial activity against Bacillus subtilis ATCC 6633 compared to separately MWCNT-C(C=O)-OH and CuTAM. - Abstract: In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the I{sub D}/I{sub G} ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

  15. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  16. Application of Calixarenes as Macrocyclic Ligands for Uranium(VI: A Review

    Directory of Open Access Journals (Sweden)

    Katarzyna Kiegiel

    2013-01-01

    Full Text Available Calixarenes represent a well-known family of macrocyclic molecules with broad range of potential applications in chemical, analytical, and engineering materials fields. This paper covers the use of calixarenes as complexing agents for uranium(VI. The high effectiveness of calix[6]arenes in comparison to other calixarenes in uranium(VI separation process is also presented. Processes such as liquid-liquid extraction (LLE, liquid membrane (LM separation, and ion exchange are considered as potential fields for application of calixarenes as useful agents for binding UO22+ for effective separation from aqueous solutions containing other metal components.

  17. Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles.

    Science.gov (United States)

    Givaja, Gonzalo; Volpe, Manuel; Leeland, James W; Edwards, Michael A; Young, Thomas K; Darby, S Barnie; Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Wolowska, Joanna; McInnes, Eric J L; Schröder, Martin; Love, Jason B

    2007-01-01

    The syntheses, characterisation and complexation reactions of a series of binucleating Schiff-base calixpyrrole macrocycles are described. The acid-templated [2+2] condensations between meso-disubstituted diformyldipyrromethanes and o-phenylenediamines generate the Schiff-base pyrrolic macrocycles H(4)L(1) to H(4)L(6) upon basic workup. The single-crystal X-ray structures of both H(4)L(3).2 EtOH and H(4)L(6).H2O confirm that [2+2] cyclisation has occurred, with either EtOH or H2O hydrogen-bonded within the macrocyclic cleft. A series of complexation reactions generate the dipalladium [Pd2(L)] (L=L(1) to L(5)), dinickel [Ni2(L(1))] and dicopper [Cu2(L)] (L=L(1) to L(3)) complexes. All of these complexes have been structurally characterised in the solid state and are found to adopt wedged structures that are enforced by the rigidity of the aryl backbone to give a cleft reminiscent of the structures of Pacman porphyrins. The binuclear nickel complexes [Ni2(mu-OMe)2Cl2(HOMe)2(H(4)L(1))] and [Ni2(mu-OH)2Cl2(HOMe)(H(4)L(5))] have also been prepared, although in these cases the solid-state structures show that the macrocyclic ligand remains protonated at the pyrrolic nitrogen atoms, and the Ni(II) cations are therefore co-ordinated by the imine nitrogen atoms only to give an open conformation for the complex. The dicopper complex [Cu2(L(3))] was crystallised in the presence of pyridine to form the adduct [Cu2(py)(L(3))], in which, in the solid state, the pyridine ligand is bound within the binuclear molecular cleft. Reaction between H(4)L(1) and [Mn(thf){N(SiMe(3))2}2] results in clean formation of the dimanganese complex [Mn2(L(1))], which, upon crystallisation, formed the mixed-valent complex [Mn2(mu-OH)(L(1))] in which the hydroxo ligand bridges the metal centres within the molecular cleft.

  18. Molecular Rearrangement of an Aza-Scorpiand Macrocycle Induced by pH: A Computational Study

    Directory of Open Access Journals (Sweden)

    Jesus Vicente De Julián-Ortiz

    2016-07-01

    Full Text Available Rearrangements and their control are a hot topic in supramolecular chemistry due to the possibilities that these phenomena open in the design of synthetic receptors and molecular machines. Macrocycle aza-scorpiands constitute an interesting system that can reorganize their spatial structure depending on pH variations or the presence of metal cations. In this study, the relative stabilities of these conformations were predicted computationally by semi-empirical and density functional theory approximations, and the reorganization from closed to open conformations was simulated by using the Monte Carlo multiple minimum method.

  19. Biomechanical Assessment of the Strength of Volleyball Players in Different Stages of the Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Śliwa Marcin

    2015-09-01

    Full Text Available Introduction. In order to help volleyball players achieve superior results, their coaches are constantly seeking new training methods. One of the methods used to improve the effectiveness of the training that is being implemented is conducting tests which make it possible to assess the player’s locomotor system in terms of its motor and biomechanical functions. The aim of the study was to determine the torque of the knee flexor and extensor muscles of volleyball players in three stages of the annual macrocycle.

  20. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Wen-Jian [National Cancer Inst., Frederick, MD (United States); Park, Jung-Eun [National Cancer Inst., Bethesda, MD (United States); Grant, Robert [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lai, Christopher C. [National Cancer Inst., Frederick, MD (United States); Kelley, James A. [National Cancer Inst., Frederick, MD (United States); Yaffe, Michael B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lee, Kyung S. [National Cancer Inst., Bethesda, MD (United States); Burke, Terrence R. [National Cancer Inst., Frederick, MD (United States)

    2015-07-07

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  1. Kinetic Analysis for Macrocyclizations Involving Anionic Template at the Transition State

    Directory of Open Access Journals (Sweden)

    Vicente Martí-Centelles

    2012-01-01

    competitive oligomerization/polymerization processes yielding undesired oligomeric/polymeric byproducts. The effect of anions has also been included in the kinetic models, as they can act as catalytic templates in the transition state reducing and stabilizing the transition state. The corresponding differential equation systems for each kinetic model can be solved numerically. Through a comprehensive analysis of these results, it is possible to obtain a better understanding of the different parameters that are involved in the macrocyclization reaction mechanism and to develop strategies for the optimization of the desired processes.

  2. Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

    Science.gov (United States)

    Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

    2015-03-15

    Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Improved selectivity for Pb(II) by sulfur, selenium and tellurium analogues of 1,8-anthraquinone-18-crown-5: synthesis, spectroscopy, X-ray crystallography and computational studies.

    Science.gov (United States)

    Mariappan, Kadarkaraisamy; Alaparthi, Madhubabu; Hoffman, Mariah; Rama, Myriam Alcantar; Balasubramanian, Vinothini; John, Danielle M; Sykes, Andrew G

    2015-07-14

    We report here a series of heteroatom-substituted macrocycles containing an anthraquinone moiety as a fluorescent signaling unit and a cyclic polyheteroether chain as the receptor. Sulfur, selenium, and tellurium derivatives of 1,8-anthraquinone-18-crown-5 (1) were synthesized by reacting sodium sulfide (Na2S), sodium selenide (Na2Se) and sodium telluride (Na2Te) with 1,8-bis(2-bromoethylethyleneoxy)anthracene-9,10-dione in a 1 : 1 ratio. The optical properties of the new compounds are examined and the sulfur and selenium analogues produce an intense green emission enhancement upon association with Pb(II) in acetonitrile. Selectivity for Pb(II) is markedly improved as compared to the oxygen analogue 1 which was also competitive for Ca(II) ion. UV-Visible and luminescence titrations reveal that 2 and 3 form 1 : 1 complexes with Pb(II), confirmed by single-crystal X-ray studies where Pb(II) is complexed within the macrocycle through coordinate covalent bonds to neighboring carbonyl, ether and heteroether donor atoms. Cyclic voltammetry of 2-8 showed classical, irreversible oxidation potentials for sulfur, selenium and tellurium heteroethers in addition to two one-electron reductions for the anthraquinone carbonyl groups. DFT calculations were also conducted on 1, 2, 3, 6, 6 + Pb(II) and 6 + Mg(II) to determine the trend in energies of the HOMO and the LUMO levels along the series.

  4. Marginal Assessment of Crowns by the Aid of Parallel Radiography

    Directory of Open Access Journals (Sweden)

    Farnaz Fattahi

    2015-03-01

    Full Text Available Introduction: Marginal adaptation is the most critical item in long-term prognosis of single crowns. This study aimed to assess the marginal quality as well asthe discrepancies in marginal integrity of some PFM single crowns of posterior teeth by employing parallel radiography in Shiraz Dental School, Shiraz, Iran. Methods: In this descriptive study, parallel radiographies were taken from 200 fabricated PFM single crowns of posterior teeth after cementation and before discharging the patient. To calculate the magnification of the images, a metallic sphere with the thickness of 4 mm was placed in the direction of the crown margin on the occlusal surface. Thereafter, the horizontal and vertical space between the crown margins, the margin of preparations and also the vertical space between the crown margin and the bone crest were measured by using digital radiological software. Results: Analysis of data by descriptive statistics revealed that 75.5% and 60% of the cases had more than the acceptable space (50µm in the vertical (130±20µm and horizontal (90±15µm dimensions, respectively. Moreover, 85% of patients were found to have either horizontal or vertical gap. In 77% of cases, the margins of crowns invaded the biologic width in the mesial and 70% in distal surfaces. Conclusion: Parallel radiography can be expedient in the stage of framework try-in to yield some important information that cannot be obtained by routine clinical evaluations and may improve the treatment prognosis

  5. Effect of posterior crown margin placement on gingival health.

    Science.gov (United States)

    Reitemeier, Bernd; Hänsel, Kristina; Walter, Michael H; Kastner, Christian; Toutenburg, Helge

    2002-02-01

    The clinical impact of posterior crown margin placement on gingival health has not been thoroughly quantified. This study evaluated the effect of posterior crown margin placement with multivariate analysis. Ten general dentists reviewed 240 patients with 480 metal-ceramic crowns in a prospective clinical trial. The alloy was randomly selected from 2 high gold, 1 low gold, and 1 palladium alloy. Variables were the alloy used, oral hygiene index score before treatment, location of crown margins at baseline, and plaque index and sulcus bleeding index scores recorded for restored and control teeth after 1 year. The effect of crown margin placement on sulcular bleeding and plaque accumulation was analyzed with regression models (Prisk of bleeding at intrasulcular posterior crown margins was approximately twice that at supragingival margins. Poor oral hygiene before treatment and plaque also were associated with sulcular bleeding. Facial sites exhibited a lower probability of sulcular bleeding than lingual surfaces. Type of alloy did not influence sulcular bleeding. In this study, placement of crown margins was one of several parameters that affected gingival health.

  6. Review of Alberta Crown Crude Oil Marketing Program

    International Nuclear Information System (INIS)

    Crandall, G. R.; Kromm, R. B.

    1999-01-01

    This report contains an independent evaluation of the operations of the private marketing agents that are currently marketing the Alberta Crown's share of royalty crude oil. The evaluation includes a review of pricing performance, working relationship, current issues and the overall performance of the marketing arrangements during the fiscal years of 1997 and 1998. Overall, the outsourcing of sales of Crown production to agents is judged to be successful. For example, it has been noted that agents are becoming more aggressive in maintaining and increasing their margins. On the other hand, the increased level of aggressiveness in marketing, while tending to maximize Crown revenues, is also creating a potential conflict on how margins should be shared between the Crown and its agents. Also, there has been evidence of some management issues between the agents and the Crown concerning the extent to which the Crown should share in any increased value which the agent generates by increased third party marketing activities. These differences need to be addressed in order to maintain the strong performance of the marketing program. The consultants also recommend additional guidelines on risk management issues that more clearly define the Crown's risk tolerance. 2 tabs., 4 figs

  7. Unique case of a geminated supernumerary tooth with trifid crown

    International Nuclear Information System (INIS)

    Ather, Amber; Ather, Hunaiza; Sheth, Sanket Milan; Muliya, Vidya Saraswathi

    2012-01-01

    Gemination, a relatively uncommon dental anomaly, is characterized by its peculiar representation as a tooth with a bifid crown and a common root and root canal. It usually occurs in primary dentition. To come across gemination in a supernumerary tooth is a rare phenomenon. The purpose of this paper is to present a unique case of hyperdontia wherein gemination in an impacted supernumerary tooth resulted in a trifid crown unlike the usual bifid crown. The role of conventional radiographs as well as computed tomography, to accurately determine the morphology and spatial location, and to arrive at a diagnosis, is also emphasized in this paper.

  8. Composite fuselage crown panel manufacturing technology

    Science.gov (United States)

    Willden, Kurtis; Metschan, S.; Grant, C.; Brown, T.

    1992-01-01

    Commercial fuselage structures contain significant challenges in attempting to save manufacturing costs with advanced composite technology. Assembly issues, material costs, and fabrication of elements with complex geometry are each expected to drive the cost of composite fuselage structures. Boeing's efforts under the NASA ACT program have pursued key technologies for low-cost, large crown panel fabrication. An intricate bond panel design and manufacturing concepts were selected based on the efforts of the Design Build Team (DBT). The manufacturing processes selected for the intricate bond design include multiple large panel fabrication with the Advanced Tow Placement (ATP) process, innovative cure tooling concepts, resin transfer molding of long fuselage frames, and utilization of low-cost material forms. The process optimization for final design/manufacturing configuration included factory simulations and hardware demonstrations. These efforts and other optimization tasks were instrumental in reducing cost by 18 percent and weight by 45 percent relative to an aluminum baseline. The qualitative and quantitative results of the manufacturing demonstrations were used to assess manufacturing risks and technology readiness.

  9. The energetic characterization of pineapple crown leaves.

    Science.gov (United States)

    Braga, R M; Queiroga, T S; Calixto, G Q; Almeida, H N; Melo, D M A; Melo, M A F; Freitas, J C O; Curbelo, F D S

    2015-12-01

    Energetic characterization of biomass allows for assessing its energy potential for application in different conversion processes into energy. The objective of this study is to physicochemically characterize pineapple crown leaves (PC) for their application in energy conversion processes. PC was characterized according to ASTM E871-82, E1755-01, and E873-82 for determination of moisture, ash, and volatile matter, respectively; the fixed carbon was calculated by difference. Higher heating value was determined by ASTM E711-87 and ash chemical composition was determined by XRF. The thermogravimetric and FTIR analyses were performed to evaluate the thermal decomposition and identify the main functional groups of biomass. PC has potential for application in thermochemical processes, showing high volatile matter (89.5%), bulk density (420.8 kg/m(3)), and higher heating value (18.9 MJ/kg). The results show its energy potential justifying application of this agricultural waste into energy conversion processes, implementing sustainability in the production, and reducing the environmental liabilities caused by its disposal.

  10. Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles

    Science.gov (United States)

    Zhang, Ting; Zhou, Li-Peng; Guo, Xiao-Qing; Cai, Li-Xuan; Sun, Qing-Fu

    2017-06-01

    Container-molecules are attractive to chemists due to their unique structural characteristics comparable to enzymes and receptors in nature. We report here a family of artificial self-assembled macrocyclic containers that feature induced-fit transformations in response to different anionic guests. Five metal-organic macrocycles with empirical formula of MnL2n (M=Metal L=Ligand n=3, 4, 5, 6, 7) are selectively obtained starting from one simple benzimidazole-based ligand and square-planar palladium(II) ions, either by direct anion-adaptive self-assembly or induced-fit transformations. Hydrogen-bonding interactions between the inner surface of the macrocycles and the anionic guests dictate the shape and size of the product. A comprehensive induced-fit transformation map across all the MnL2n species is drawn, with a representative reconstitution process from Pd7L14 to Pd3L6 traced in detail, revealing a gradual ring-shrinking mechanism. We envisage that these macrocyclic molecules with adjustable well-defined hydrogen-bonding pockets will find wide applications in molecular sensing or catalysis.

  11. Characterization and crystal structure of a 17-membered macrocyclic Schiff base compound MeO-sal-pn-bn

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Ghoran, S.H.; Rohlíček, Jan; Dušek, Michal

    2015-01-01

    Roč. 56, č. 2 (2015), s. 259-265 ISSN 0022-4766 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : macrocyclic * Schiff base * spectroscopy * powder diffraction * orthorhombic Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.536, year: 2015

  12. Copper(i)-induced amplification of a [2]catenane in a virtual dynamic library of macrocyclic alkenes

    NARCIS (Netherlands)

    Berrocal, J.A.; Nieuwenhuizen, M.M.L.; Mandolini, L.; Meijer, E.W.; Di Stefano, S.

    2014-01-01

    Olefin cross-metathesis of diluted dichloromethane solutions (=0.15 M) of the 28-membered macrocyclic alkene C1, featuring a 1,10-phenanthroline moiety in the backbone, as well as of catenand 1, composed of two identical interlocked C1 units, generates families of noninterlocked oligomers Ci. The

  13. Organic carbonates as solvents in macrocyclic Mn(III) salen catalyzed asymmetric epoxidation of non-functionalized olefins

    Czech Academy of Sciences Publication Activity Database

    Maity, N. Ch.; Rao, G. V. S.; Prathap, Kaniraj Jeya; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Bajaj, H. C.

    2013-01-01

    Roč. 366, January (2013), s. 380-389 ISSN 1381-1169 Institutional support: RVO:61388963 Keywords : asymmetric epoxidation * organic carbonate * macrocyclic Mn(III) salen complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2013

  14. Acetylene–ammonia–18-crown-6 (1/2/1

    Directory of Open Access Journals (Sweden)

    Tobias Grassl

    2012-10-01

    Full Text Available The title compound, C2H2·C12H24O6·2NH3, was formed by co-crystallization of 18-crown-6 and acetylene in liquid ammonia. The 18-crown-6 molecule has threefold rotoinversion symmetry. The acteylene molecule lies on the threefold axis and the whole molecule is generated by an inversion center. The two ammonia molecules are also located on the threefold axis and are related by inversion symmetry. In the crystal, the ammonia molecules are located below and above the crown ether plane and are connected by intermolecular N—H...O hydrogen bonds. The acetylene molecules are additionally linked by weak C—H...N interactions into chains that propagate in the direction of the crystallographic c axis. The 18-crown-6 molecule [occupancy ratio 0.830 (4:0.170 (4] is disordered and was refined using a split model.

  15. Mandibular molar crown-topography, a biological predisposing ...

    African Journals Online (AJOL)

    Mandibular molar crown-topography, a biological predisposing factor to development of caries – a post-mortem analysis of 2500 extracted lower permanent molars at the dental centre, University of Benin teaching hospital.

  16. Sentencing dangerous offenders: policy and practice in the Crown Court

    OpenAIRE

    Henham, R

    2001-01-01

    Analysis of Crown Courts' use of protective sentencing powers under s.80(2)(b), s.85, and s.109 of 2000 Act and whether preference for s.85 reflects fundamental flaw in leaving determination of "dangerousness" to judiciary.

  17. Fractal approach to computer-analytical modelling of tree crown

    International Nuclear Information System (INIS)

    Berezovskaya, F.S.; Karev, G.P.; Kisliuk, O.F.; Khlebopros, R.G.; Tcelniker, Yu.L.

    1993-09-01

    In this paper we discuss three approaches to the modeling of a tree crown development. These approaches are experimental (i.e. regressive), theoretical (i.e. analytical) and simulation (i.e. computer) modeling. The common assumption of these is that a tree can be regarded as one of the fractal objects which is the collection of semi-similar objects and combines the properties of two- and three-dimensional bodies. We show that a fractal measure of crown can be used as the link between the mathematical models of crown growth and light propagation through canopy. The computer approach gives the possibility to visualize a crown development and to calibrate the model on experimental data. In the paper different stages of the above-mentioned approaches are described. The experimental data for spruce, the description of computer system for modeling and the variant of computer model are presented. (author). 9 refs, 4 figs

  18. Heavy metal accumulation in Melilotus officinalis under crown Olea ...

    African Journals Online (AJOL)

    STORAGESEVER

    2008-11-05

    Nov 5, 2008 ... crown Olea europaea L forest irrigated with wastewater. S. Seif Amiri1, H. ... mainly because they are non-biodegradable, non-thermo- ... Soils, as filters of ... transportation to the laboratory, soil samples were air dried, crush-.

  19. Macrocyclic receptor showing extremely high Sr(II)/Ca(II) and Pb(II)/Ca(II) selectivities with potential application in chelation treatment of metal intoxication.

    Science.gov (United States)

    Ferreirós-Martínez, Raquel; Esteban-Gómez, David; Tóth, Éva; de Blas, Andrés; Platas-Iglesias, Carlos; Rodríguez-Blas, Teresa

    2011-04-18

    Herein we report a detailed investigation of the complexation properties of the macrocyclic decadentate receptor N,N'-Bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6) toward different divalent metal ions [Zn(II), Cd(II), Pb(II), Sr(II), and Ca(II)] in aqueous solution. We have found that this ligand is especially suited for the complexation of large metal ions such as Sr(II) and Pb(II), which results in very high Pb(II)/Ca(II) and Pb(II)/Zn(II) selectivities (in fact, higher than those found for ligands widely used for the treatment of lead poisoning such as ethylenediaminetetraacetic acid (edta)), as well as in the highest Sr(II)/Ca(II) selectivity reported so far. These results have been rationalized on the basis of the structure of the complexes. X-ray crystal diffraction, (1)H and (13)C NMR spectroscopy, as well as theoretical calculations at the density functional theory (B3LYP) level have been performed. Our results indicate that for large metal ions such as Pb(II) and Sr(II) the most stable conformation is Δ(δλδ)(δλδ), while for Ca(II) our calculations predict the Δ(λδλ)(λδλ) form being the most stable one. The selectivity that bp18c6(2-) shows for Sr(II) over Ca(II) can be attributed to a better fit between the large Sr(II) ions and the relatively large crown fragment of the ligand. The X-ray crystal structure of the Pb(II) complex shows that the Δ(δλδ)(δλδ) conformation observed in solution is also maintained in the solid state. The Pb(II) ion is endocyclically coordinated, being directly bound to the 10 donor atoms of the ligand. The bond distances to the donor atoms of the pendant arms (2.55-2.60 Å) are substantially shorter than those between the metal ion and the donor atoms of the crown moiety (2.92-3.04 Å). This is a typical situation observed for the so-called hemidirected compounds, in which the Pb(II) lone pair is stereochemically active. The X-ray structures of the Zn(II) and Cd(II) complexes show that

  20. Consequences of crown shortening canine teeth in Greenland sled dogs

    DEFF Research Database (Denmark)

    Kortegaard, H E; Anthony Knudsen, T; Dahl, S

    2015-01-01

    OBJECTIVES: To evaluate the consequences of crown shortening, focusing on the prevalence of pulp exposure and periapical pathology in Greenland sled dogs that had had their canine crowns shortened at an early age. METHODS: Five cadaver heads and 54 sled dogs underwent an oral examination for dental...... fractures and pulp exposure of canines. All canines were radiographed and evaluated for periapical pathology. RESULTS: The prevalence of canine pulp exposure in 12 (5 heads and 7 dogs) crown shortened dogs was 91 · 7%, and 21 · 3% in 47 not-crown shortened dogs. A significant (P pulp...... exposure of the canines in the crown shortened group compared to the not-crown shortened group was seen with a relative risk of 4 · 3 on a dog basis and a relative risk of 12 · 2 on a tooth basis. In dogs with pulp exposure of canines (n = 51) the prevalence of periapical pathology was 82 · 4%, but only 0...

  1. Fracture load of different crown systems on zirconia implant abutments.

    Science.gov (United States)

    Albrecht, T; Kirsten, A; Kappert, H F; Fischer, H

    2011-03-01

    The purpose of this study was to evaluate the fracture load of single zirconia abutment restorations using different veneering techniques and materials. The abutment restorations were divided into 6 groups with 20 samples each: test abutments (control group A), lithium disilicate ceramic crowns bonded on incisor abutments (group B), leucite ceramic crowns bonded on incisor abutments (group C), premolar abutments directly veneered with a fluor apatite ceramic (group D (layered) and group E (pressed)) and premolar abutments bonded with lithium disilicate ceramic crowns (group F). The fracture load of the restorations was evaluated using a universal testing machine. Half of each group was artificially aged (chewing simulation and thermocycling) before evaluating the fracture load with the exception of the test abutments. The fracture load of the test abutments was 705 ± 43N. Incisor abutments bonded with lithium disilicate or leucite ceramic crowns (groups B and C) showed fracture loads of about 580N. Premolar restorations directly veneered with fluor apatite ceramic (groups D and E) showed fracture loads of about 850N. Premolar restorations bonded with lithium disilicate ceramic crowns (group F) showed fracture loads of about 1850N. The artificial ageing showed no significant influence on the strength of the examined restorations. All ceramic crowns made of lithium disilicate glass-ceramic, adhesively bonded to premolar abutments showed the highest fracture loads in this study. However, all tested groups can withstand physiological bite forces. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  2. Root-Crown Relations of Young Sugar Maple and Yellow Birch

    Science.gov (United States)

    Carl H. Tubbs

    1977-01-01

    Young forest-grown sugar maple and yellow birch (1 to 6 inches d.b.h.) crowns were mapped and roots excavated. Crown dimensions were compared. Sugar maple roots usually terminated within a few feet of the crown perimeter. Yellow birch roots frequently terminated well outside crown perimeters and roots of birch were more irregularly distributed than those of maple....

  3. 30 CFR 250.404 - What are the requirements for the crown block?

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false What are the requirements for the crown block... General Requirements § 250.404 What are the requirements for the crown block? You must have a crown block safety device that prevents the traveling block from striking the crown block. You must check the device...

  4. Macrocyclic chelator-coupled gastrin-based radiopharmaceuticals for targeting of gastrin receptor-expressing tumours

    International Nuclear Information System (INIS)

    Good, Stephan; Wang, Xuejuan; Maecke, Helmut R.; Walter, Martin A.; Mueller-Brand, Jan; Waser, Beatrice; Reubi, Jean-Claude; Behe, Martin P.

    2008-01-01

    Diethylenetriamine-pentaacetic acid (DTPA)-coupled minigastrins are unsuitable for therapeutic application with the available β-emitting radiometals due to low complex stability. Low tumour-to-kidney ratio of the known radiopharmaceuticals is further limiting their potency. We used macrocyclic chelators for coupling to increase complex stability, modified the peptide sequence to enhance radiolytic stability and studied tumour-to-kidney ratio and metabolic stability using 111 In-labelled derivatives. Gastrin derivatives with decreasing numbers of glutamic acids were synthesised using 111 In as surrogate for therapeutic radiometals for in vitro and in vivo studies. Gastrin receptor affinities of the nat In-metallated compounds were determined by receptor autoradiography using 125 I-CCK as radioligand. Internalisation was evaluated in AR4-2J cells. Enzymatic stability was determined by incubating the 111 In-labelled peptides in human serum. Biodistribution was performed in AR4-2J-bearing Lewis rats. IC 50 values of the nat In-metallated gastrin derivatives vary between 1.2 and 4.8 nmol/L for all methionine-containing derivatives. Replacement of methionine by norleucine, isoleucine, methionine-sulfoxide and methionine-sulfone resulted in significant decrease of receptor affinity (IC 50 between 9.9 and 1,195 nmol/L). All cholecystokinin receptor affinities were >100 nmol/L. All 111 In-labelled radiopeptides showed receptor-specific internalisation. Serum mean-life times varied between 2.0 and 72.6 h, positively correlating with the number of Glu residues. All 111 In-labelled macrocyclic chelator conjugates showed higher tumour-to-kidney ratios after 24 h (0.37-0.99) compared to 111 In-DTPA-minigastrin 0(0.05). Tumour wash out between 4 and 24 h was low. Imaging studies confirmed receptor-specific blocking of the tumour uptake. Reducing the number of glutamates increased tumour-to-kidney ratio but resulted in lower metabolic stability. The properties of the macrocyclic

  5. Macrocyclic chelator-coupled gastrin-based radiopharmaceuticals for targeting of gastrin receptor-expressing tumours

    Energy Technology Data Exchange (ETDEWEB)

    Good, Stephan; Wang, Xuejuan; Maecke, Helmut R. [University Hospital Basel, Division of Radiological Chemistry, Basel (Switzerland); Walter, Martin A.; Mueller-Brand, Jan [University Hospital, Institute of Nuclear Medicine, Basel (Switzerland); Waser, Beatrice; Reubi, Jean-Claude [University of Berne, Department of Pathology, Bern (Switzerland); Behe, Martin P. [Philipps-University of Marburg, Department of Nuclear Medicine, Marburg (Germany)

    2008-10-15

    Diethylenetriamine-pentaacetic acid (DTPA)-coupled minigastrins are unsuitable for therapeutic application with the available {beta}-emitting radiometals due to low complex stability. Low tumour-to-kidney ratio of the known radiopharmaceuticals is further limiting their potency. We used macrocyclic chelators for coupling to increase complex stability, modified the peptide sequence to enhance radiolytic stability and studied tumour-to-kidney ratio and metabolic stability using {sup 111}In-labelled derivatives. Gastrin derivatives with decreasing numbers of glutamic acids were synthesised using {sup 111}In as surrogate for therapeutic radiometals for in vitro and in vivo studies. Gastrin receptor affinities of the {sup nat}In-metallated compounds were determined by receptor autoradiography using {sup 125}I-CCK as radioligand. Internalisation was evaluated in AR4-2J cells. Enzymatic stability was determined by incubating the {sup 111}In-labelled peptides in human serum. Biodistribution was performed in AR4-2J-bearing Lewis rats. IC{sub 50} values of the {sup nat}In-metallated gastrin derivatives vary between 1.2 and 4.8 nmol/L for all methionine-containing derivatives. Replacement of methionine by norleucine, isoleucine, methionine-sulfoxide and methionine-sulfone resulted in significant decrease of receptor affinity (IC{sub 50} between 9.9 and 1,195 nmol/L). All cholecystokinin receptor affinities were >100 nmol/L. All {sup 111}In-labelled radiopeptides showed receptor-specific internalisation. Serum mean-life times varied between 2.0 and 72.6 h, positively correlating with the number of Glu residues. All {sup 111}In-labelled macrocyclic chelator conjugates showed higher tumour-to-kidney ratios after 24 h (0.37-0.99) compared to {sup 111}In-DTPA-minigastrin 0(0.05). Tumour wash out between 4 and 24 h was low. Imaging studies confirmed receptor-specific blocking of the tumour uptake. Reducing the number of glutamates increased tumour-to-kidney ratio but resulted in

  6. Synthesis and optoelectronic properties of a monodispersed macrocycle oligomer consisting of three triarylamine units

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Qinggang, E-mail: gangq0172@163.com [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, College of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu Road, Pukou District, Nanjing 210044 (China); Qian, Haiyan, E-mail: qianhaiy@163.com [College of Material Science and Technology, Nanjing University of Technology, 5 Xinmofan Road, Nanjing 210009 (China); Zhou, Yonghui; Li, Jun; Xiao, Huining [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, College of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu Road, Pukou District, Nanjing 210044 (China)

    2012-08-15

    A monodispersed macrocyclic oligomer constructed by three triarylmine units ((TPAT){sub 3}) was designed and readily synthesized from the monomer of 3-(4 Prime -(phenyl(4 Double-Prime -methylphenyl)amino)-phenyl)pentan-3-ol (TPAT) by means of a simple Friedel-Crafts alkylation reaction. The structure of the resultant macrocycle was examined using FT-IR, NMR and MALDI-TOF mass spectroscopy. Compared with 1,10-bis(di-4-tolylaminophenyl) cyclohexane (TAPC) and tri-p-tolylamine (TTA), (TPAT){sub 3} possesses the three-dimensional chair conformation and the higher T{sub g}. In the photoluminescence (PL) spectrum of (TPAT){sub 3} film, there are no excimer emission peaks in the range of 400-550 nm region as those of TAPC and TTA. Besides an EL peak at 386 nm, the single-layer device occured only the 438 nm excimer emission peak, whose intensity increased with the excitation voltage increase. Using 1,3,5-Tris(N-phenylbenzimidazol-2-yl)-benzene (TPBI) as the electron-transporting layer, the resulting double-layer device ITO/(TPAT){sub 3} (40 nm)/TPBI (40 nm)/Mg:Ag (10:1; 50 nm)/Ag (100 nm) only exhibited a 438 nm maximum symmetrical emission peak under an excitation voltage of 14 V. However, as the applied voltage was increased from 14 V to 19 V, the intensity of the symmetrical curve with a 468 nm peak from exciplex emission gets stronger and stronger. In fact, the resultant emission curve was asymmetrical, due to the overlap of two symmetrical curves with 438 nm and 468 nm peaks, respectively. The maximum luminance and luminous efficiency are 2240 cd m{sup -2} at 18.8 V and 1.73 cd A{sup -1} at 1878 cd m{sup -2} (13.9 V). Highlights: Black-Right-Pointing-Pointer The monodispersed macrocyclic oligomer constructed by three triarylamine units was synthesized and characterized. Black-Right-Pointing-Pointer The PL of (TPAT){sub 3} film does not emerge TAPC and TTA's emission peaks of over 400 nm region. Black-Right-Pointing-Pointer The 438 nm emission peak was found from

  7. Safety and clinical efficacy of tenvermectin, a novel antiparasitic 16-membered macrocyclic lactone antibiotics.

    Science.gov (United States)

    Fei, Chenzhong; She, Rufeng; Li, Guiyu; Zhang, Lifang; Fan, Wushun; Xia, Suhan; Xue, Feiqun

    2018-05-30

    Tenvermectin (TVM) is a novel 16-membered macrocyclic lactone antibiotics, which contains component TVM A and TVM B. However there is not any report on safety and clinical efficacy of TVM for developing as a potential drug. In order to understand the part of safety and clinical efficacy of TVM, we conducted the acute toxicity test, the standard bacterial reverse mutation (Ames) test and the clinical deworming test. In the acute toxicity studies, TVM, TVM A and ivermectin (IVM) were administrated once by oral gavage to mice and rats. Results showed that the oral LD 50 values of TVM, TVM A and IVM in mice were 74.41, 106.95 and 53.06 mg/kg respectively. The oral LD 50 values of TVM and TVM A in rats were determined to be 164.22 and 749.34 mg/kg respectively. TVM and IVM are moderately toxic substances, meanwhile the TVM A belongs to low toxic compounds, implying that the acute toxicity is highly related to the length of side chain of TVM at position C25. In the Ames test, results showed that TVM did not induce mutagenicity in Salmonella typhimurium TA97a, TA98, TA100, TA102 and TA1535 with and without metabolic activation system, speculating that the mutagenicity is probably not related to the side chain at position C25 of 16-membered macrocyclic lactone antibiotics. In the efficacy trail of TVM against swine nematodes, growing pigs natural infection of Ascaris suum and Trichuris suis were treated with a single subcutaneous injection 0.3 mg/kg b.w.. Results showed that TVM and IVM had excellent effect in expelling Ascaris suum, and TVM had potential efficacy against Trichuris suis, however IVM had no effect on Trichuris suis. This study suggests that the side chain of TVM at position C25 may have important biological functions, which is one of the key sites of the studies on structure-activity relationship of 16-membered macrocyclic lactone compounds. TVM is a new compound exhibited some advantages worthy of developing. Copyright © 2018 Elsevier B.V. All

  8. Comparison of column chromatographic and precipitation methods for the purification of a macrocyclic polyether extractant

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, M.L.; Felinto, C.; Rhoads, S.; Clapper, M.; Finch, J.W.; Hay, B.P.

    1999-11-01

    Column chromatography on aminopropyl-derivatized silica and precipitation of a complex with perchloric acid have been evaluated as methods for the purification of di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6), a compound frequently employed for the selective extraction of strontium from acidic nitrate media. Both methods are shown to provide a simple and effective means of eliminating inactive sample components (i.e., impurities or stereoisomers incapable of extracting strontium) from the crown ether and enriching the material in 4(z),4{prime}(z) cis-syn-cis DtBuCH18C6, a stereoisomer capable of highly efficient strontium extraction.

  9. Comparison of column chromatographic and precipitation methods for the purification of a macrocyclic polyether extractant

    International Nuclear Information System (INIS)

    Dietz, M.L.; Felinto, C.; Rhoads, S.; Clapper, M.; Finch, J.W.; Hay, B.P.

    1999-01-01

    Column chromatography on aminopropyl-derivatized silica and precipitation of a complex with perchloric acid have been evaluated as methods for the purification of di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6), a compound frequently employed for the selective extraction of strontium from acidic nitrate media. Both methods are shown to provide a simple and effective means of eliminating inactive sample components (i.e., impurities or stereoisomers incapable of extracting strontium) from the crown ether and enriching the material in 4(z),4 prime(z) cis-syn-cis DtBuCH18C6, a stereoisomer capable of highly efficient strontium extraction

  10. Suitability of Secondary PEEK Telescopic Crowns on Zirconia Primary Crowns: The Influence of Fabrication Method and Taper

    Directory of Open Access Journals (Sweden)

    Susanne Merk

    2016-11-01

    Full Text Available This study investigates the retention load (RL between ZrO2 primary crowns and secondary polyetheretherketone (PEEK crowns made by different fabrication methods with three different tapers. Standardized primary ZrO2 crowns were fabricated with three different tapers: 0°, 1°, and 2° (n = 10/group. Ten secondary crowns were fabricated (i milled from breCam BioHPP blanks (PM; (ii pressed from industrially fabricated PEEK pellets (PP (BioHPP Pellet; or (iii pressed from granular PEEK (PG (BioHPP Granulat. One calibrated operator adjusted all crowns. In total, the RL of 90 secondary crowns were measured in pull-off tests at 50 mm/min, and each specimen was tested 20 times. Two- and one-way ANOVAs followed by a Scheffé’s post-hoc test were used for data analysis (p < 0.05. Within crowns with a 0° taper, the PP group showed significantly higher retention load values compared with the other groups. Among the 1° taper, the PM group presented significantly lower retention loads than the PP group. However, the pressing type had no impact on the results. Within the 2° taper, the fabrication method had no influence on the RL. Within the PM group, the 2° taper showed significantly higher retention load compared with the 1° taper. The taper with 0° was in the same range value as the 1° and 2° tapers. No impact of the taper on the retention value was observed between the PP groups. Within the PG groups, the 0° taper presented significantly lower RL than the 1° taper, whereas the 2° taper showed no differences. The fabrication method of the secondary PEEK crowns and taper angles showed no consistent effect within all tested groups.

  11. Design, synthesis, X-ray studies, and biological evaluation of novel macrocyclic HIV-1 protease inhibitors involving the P1'-P2' ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Arun K.; Sean Fyvie, W.; Brindisi, Margherita; Steffey, Melinda; Agniswamy, Johnson; Wang, Yuan-Fang; Aoki, Manabu; Amano, Masayuki; Weber, Irene T.; Mitsuya, Hiroaki

    2017-11-01

    Design, synthesis, and evaluation of a new class of HIV-1 protease inhibitors containing diverse flexible macrocyclic P1'-P2' tethers are reported. Inhibitor 5a with a pyrrolidinone-derived macrocycle exhibited favorable enzyme inhibitory and antiviral activity (Ki = 13.2 nM, IC50 = 22 nM). Further incorporation of heteroatoms in the macrocyclic skeleton provided macrocyclic inhibitors 5m and 5o. These compounds showed excellent HIV-1 protease inhibitory (Ki = 62 pM and 14 pM, respectively) and antiviral activity (IC50 = 5.3 nM and 2.0 nM, respectively). Inhibitor 5o also remained highly potent against a DRV-resistant HIV-1 variant.

  12. Fast and versatile microwave-assisted intramolecular Heck reaction in peptide macrocyclization using microwave energy.

    Science.gov (United States)

    Byk, Gerardo; Cohen-Ohana, Mirit; Raichman, Daniel

    2006-01-01

    We have revisited the intramolecular Heck reaction and investigated the microwave-assisted macrocyclization on preformed peptides using a model series of ring-varying peptides acryloyl-Gly-[Gly](n)-Phe(4-I)NHR; n = 0-4. The method was applied to both solution and solid supported cyclizations. We demonstrate that the intramolecular Heck reaction can be performed in peptides both in solution and solid support using a modified domestic microwave within 1 to 30 minutes in DMF under reflux with moderate yields ranging from 15 to 25% for a scale between 2-45 mg of linear precursors. The approach was applied to the synthesis of a constrained biologically relevant peptidomimetic bearing an Arg-Gly-Asp (RGD) sequence. These results make the microwave-assisted Heck reaction an attractive renovated approach for peptidomimetics. Copyright 2006 Wiley Periodicals, Inc.

  13. Versatile protein recognition by the encoded display of multiple chemical elements on a constant macrocyclic scaffold

    Science.gov (United States)

    Li, Yizhou; De Luca, Roberto; Cazzamalli, Samuele; Pretto, Francesca; Bajic, Davor; Scheuermann, Jörg; Neri, Dario

    2018-03-01

    In nature, specific antibodies can be generated as a result of an adaptive selection and expansion of lymphocytes with suitable protein binding properties. We attempted to mimic antibody-antigen recognition by displaying multiple chemical diversity elements on a defined macrocyclic scaffold. Encoding of the displayed combinations was achieved using distinctive DNA tags, resulting in a library size of 35,393,112. Specific binders could be isolated against a variety of proteins, including carbonic anhydrase IX, horseradish peroxidase, tankyrase 1, human serum albumin, alpha-1 acid glycoprotein, calmodulin, prostate-specific antigen and tumour necrosis factor. Similar to antibodies, the encoded display of multiple chemical elements on a constant scaffold enabled practical applications, such as fluorescence microscopy procedures or the selective in vivo delivery of payloads to tumours. Furthermore, the versatile structure of the scaffold facilitated the generation of protein-specific chemical probes, as illustrated by photo-crosslinking.

  14. Tunable photophysical processes of porphyrin macrocycles on the surface of ZnO nanoparticles

    KAUST Repository

    Parida, Manas R.

    2015-01-23

    We investigated the impact of the molecular structure of cationic porphyrins on the degree of electrostatic interactions with zinc oxide nanoparticles (ZnO NPs) using steady-state and time-resolved fluorescence and transient absorption spectroscopy. Our results demonstrate that the number of cationic pyridinium units has a crucial impact on the photophysics of the porphyrin macrocycle. Fluorescence enhancement, relative to initial free porphyrin fluorescence, was found to be tuned from 3.4 to 1.3 times higher by reducing the number of cationic substituents on the porphyrin from 4 to 2. The resulting enhancement of the intensity of the fluorescence is attributed to the decrease in the intramolecular charge transfer (ICT) character between the porphyrin cavity and its meso substituent. The novel findings reported in this work provide an understanding of the key variables involved in nanoassembly, paving the way toward optimizing the interfacial chemistry of porphyrin-ZnO NP assembly for photodynamic therapy and energy conversion.

  15. Preparation and characterization of electroluminescent devices based on complexes of {beta}-diketonates of Tb{sup 3+}, Eu{sup 3+}, Gd{sup 3+} ions with macrocyclic ligands and UO{sub 2}{sup 2+} films; Preparacao e caracterizacao de dispositivos eletroluminescentes de complexos de {beta}-dicetonados de ions Tb{sup 3+}, Eu{sup 3+}, Gd{sup 3+} com ligantes macrociclicos e filmes de UO{sub 2}{sup 2+}

    Energy Technology Data Exchange (ETDEWEB)

    Gibelli, Edison Bessa

    2010-07-01

    Complexes containing Rare Earth ions are of great interest in the manufacture of electro luminescent devices as organic light emitting devices (OLED). These devices, using rare earth trivalent ions (TR{sup 3+}) as emitting centers, show high luminescence with extremely fine spectral bands due to the structure of their energy levels, long life time and high quantum efficiency. This work reports the preparation of Rare Earth {beta}-diketonate complexes (Tb{sup 3+}, Eu{sup 3+} and Gd{sup 3+}) and (tta - thenoyltrifluoroacetonate and acac - acetylacetonate) containing a ligand macrocyclic crown ether (DB18C6 - dibenzo18coroa6) and polymer films of UO{sub 2}{sup 2+}. The materials were characterized by complexometric titration with EDTA, CH elemental analysis, near infrared absorption spectroscopy, thermal analysis, X-ray diffraction (powder method) and luminescence spectroscopy. For manufacturing the OLED it was used the technique of deposition of thin films by physical vapor (PVD, Physical Vapor Deposition). (author)

  16. tetrapyrrole macrocycle

    African Journals Online (AJOL)

    ... 3(1), 17-24 (1989). CATALYTIC OXIDATION OF 3,5-DI-TERTBUTYL CATECHOL (3,5-DTBC) .... (C13) in 25 ml of methanol. To the stirred .... and electrochemical properties (15) since these properties are very similar for all the complexes.

  17. Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining.

    Science.gov (United States)

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

    2011-09-26

    A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Pólya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).

  18. Co-N-macrocyclic modified graphene with excellent electrocatalytic activity for lithium-thionyl chloride batteries

    International Nuclear Information System (INIS)

    Li, Bimei; Yuan, Zhongzhi; Xu, Ying; Liu, Jincheng

    2016-01-01

    Highlights: • A Co-N-graphene catalyst composed of CoN 4 -macrocyclic-like (CoN x ) structure is synthesized. • Co-N x -Graphene has effective electrocatalytic activity for Li/SOCl 2 batteries. • The storage stability of the catalyst is attributed to its insolubility in electrolyte. - Abstract: A mixture of cobalt phthalocyanine (CoPc) and graphene is thermally decomposed at 800 °C to synthesize a novel catalyst. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) show that the catalyst retains the lamellar structure of graphene. X-ray diffraction (XRD) reveals that the catalyst is no longer composed of CoPc and high-resolution TEM (HRTEM), X-ray photoelectron spectra (XPS) prove that Co and N elements have entered the graphene molecular structure, thus forming a Co-N x -graphene (Co-N x -G) catalyst composed of a CoN 4 -macrocyclic-like structure. This catalyst serves as an excellent catalyst of thionyl chloride (SOCl 2 ) reduction. Cyclic voltammetry and battery discharge tests reveal that Co-N x -G-800 substantially increases the discharge voltage and capacity of a Li/SOCl 2 battery. Moreover, Co-N x -G-800 exhibits stable catalytic activity during battery storage. Ultraviolet–visible spectroscopy shows that CoPc is soluble in a SOCl 2 electrolyte solution, whereas Co-N x -G-800 is not, this characteristic contributes to the stable catalytic property of Co-N x -G.

  19. Macrocyclic peptides decrease c-Myc protein levels and reduce prostate cancer cell growth.

    Science.gov (United States)

    Mukhopadhyay, Archana; Hanold, Laura E; Thayele Purayil, Hamsa; Gisemba, Solomon A; Senadheera, Sanjeewa N; Aldrich, Jane V

    2017-08-03

    The oncoprotein c-Myc is often overexpressed in cancer cells, and the stability of this protein has major significance in deciding the fate of a cell. Thus, targeting c-Myc levels is an attractive approach for developing therapeutic agents for cancer treatment. In this study, we report the anti-cancer activity of the macrocyclic peptides [D-Trp]CJ-15,208 (cyclo[Phe-D-Pro-Phe-D-Trp]) and the natural product CJ-15,208 (cyclo[Phe-D-Pro-Phe-Trp]). [D-Trp]CJ-15,208 reduced c-Myc protein levels in prostate cancer cells and decreased cell proliferation with IC 50 values ranging from 2.0 to 16 µM in multiple PC cell lines. [D-Trp]CJ-15,208 induced early and late apoptosis in PC-3 cells following 48 hours treatment, and growth arrest in the G2 cell cycle phase following both 24 and 48 hours treatment. Down regulation of c-Myc in PC-3 cells resulted in loss of sensitivity to [D-Trp]CJ-15,208 treatment, while overexpression of c-Myc in HEK-293 cells imparted sensitivity of these cells to [D-Trp]CJ-15,208 treatment. This macrocyclic tetrapeptide also regulated PP2A by reducing the levels of its phosphorylated form which regulates the stability of cellular c-Myc protein. Thus [D-Trp]CJ-15,208 represents a new lead compound for the potential development of an effective treatment of prostate cancer.

  20. Evaluation of marginal fit of 2 CAD-CAM anatomic contour zirconia crown systems and lithium disilicate glass-ceramic crown.

    Science.gov (United States)

    Ji, Min-Kyung; Park, Ji-Hee; Park, Sang-Won; Yun, Kwi-Dug; Oh, Gye-Jeong; Lim, Hyun-Pil

    2015-08-01

    This study was to evaluate the marginal fit of two CAD-CAM anatomic contour zirconia crown systems compared to lithium disilicate glass-ceramic crowns. Shoulder and deep chamfer margin were formed on each acrylic resin tooth model of a maxillary first premolar. Two CAD-CAM systems (Prettau®Zirconia and ZENOSTAR®ZR translucent) and lithium disilicate glass ceramic (IPS e.max®press) crowns were made (n=16). Each crown was bonded to stone dies with resin cement (Rely X Unicem). Marginal gap and absolute marginal discrepancy of crowns were measured using a light microscope equipped with a digital camera (Leica DFC295) magnified by a factor of 100. Two-way analysis of variance (ANOVA) and post-hoc Tukey's HSD test were conducted to analyze the significance of crown marginal fit regarding the finish line configuration and the fabrication system. The mean marginal gap of lithium disilicate glass ceramic crowns (IPS e.max®press) was significantly lower than that of the CAD-CAM anatomic contour zirconia crown system (Prettau®Zirconia) (Pmarginal discrepancy (Pmarginal gap than the CAD-CAM anatomic contour zirconia crown system (Prettau®Zirconia). In terms of absolute marginal discrepancy, the CAD-CAM anatomic contour zirconia crown system (ZENOSTAR®ZR translucent) had under-extended margin, whereas the CAD-CAM anatomic contour zirconia crown system (Prettau®Zirconia) and lithium disilicate glass ceramic crowns (IPS e.max®press) had overextended margins.

  1. Reversible Low-Light Induced Photoswitching of Crowned Spiropyran-DO3A Complexed with Gadolinium(III Ions

    Directory of Open Access Journals (Sweden)

    André Knoesen

    2012-05-01

    Full Text Available Photoswitchable spiropyran has been conjugated to the crowned ring system DO3A, which improves its solubility in dipolar and polar media and stabilizes the merocyanine isomer. Adding the lanthanide ion gadolinium(III to the macrocyclic ring system leads to a photoresponsive magnetic resonance imaging contrast agent that displays an increased spin-lattice relaxation time (T1 upon visible light stimulation. In this work, the photoresponse of this photochromic molecule to weak light illumination using blue and green light emitting diodes was investigated, simulating the emission spectra from bioluminescent enzymes. Photon emission rate of the light emitting diodes was changed, from 1.75 × 1016 photons·s−1 to 2.37 × 1012 photons·s−1. We observed a consistent visible light-induced isomerization of the merocyanine to the spiropyran form with photon fluxes as low as 2.37 × 1012 photons·s−1 resulting in a relaxivity change of the compound. This demonstrates the potential for use of the described imaging probes in low light level applications such as sensing bioluminescence enzyme activity. The isomerization behavior of gadolinium(III-ion complexed and non-complexed spiropyran-DO3A was analyzed in water and ethanol solution in response to low light illumination and compared to the emitted photon emission rate from over-expressed Gaussia princeps luciferase.

  2. Museum security and the Thomas Crown Affair.

    Energy Technology Data Exchange (ETDEWEB)

    Michaud, E. C. (Nuclear Engineering Division)

    2010-01-01

    Over the years, I've daydreamed about stealing a Vermeer, a Picasso, or Rembrandt. It tickles me, as much as watching the reboot of The Thomas Crown Affair. Why is it, do you suppose, so much fun to think about stealing a world renowned piece off the wall of a major metropolitan museum? Is it the romantic thoughts of getting away with it, walking past infrared detectors, and pressure sensors ala Indiana Jones with the sack of sand to remove the idol without triggering the security system? Is it the idea of snatching items with such fantastic prices, where the romance of possessing an item of such value is less intoxicating than selling it to a private collector for it to never be seen again? I suspect others share my daydreams as they watch theater or hear of a brazen daylight heist at museums around the world, or from private collections. Though when reality sets in, the mind of the security professional kicks in. How could one do it, why would one do it, what should you do once it's done? The main issue a thief confronts when acquiring unique goods is how to process or fence them. They become very difficult to sell because they are one-of-a-kind, easy to identify, and could lead to the people involved with the theft. The whole issue of museum security takes up an ironic twist when one considers the secretive British street artist 'Banksy'. Banksy has made a name for himself by brazenly putting up interesting pieces of art in broad daylight (though many critics don't consider his work to be art) on building walls, rooftops, or even museums. I bring him up for a interesting take on what may become a trend in museum security. In March of 2005, Banksy snuck a piece of his called 'Vandalized Oil Painting' into the Brooklyn Museum's Great Historical Painting Wing, plus 3 other pieces into major museums in New York. Within several days, 2 paintings had been torn down, but 2 stayed up much longer. In his home country of the UK, a

  3. Mesiodistal Crown Dimensions of Permanent Teeth in Bangladeshi Population

    Directory of Open Access Journals (Sweden)

    Saeed Hossain Khan

    2011-09-01

    Full Text Available Background: Variation in tooth size is influenced by genetic and environmental factors. Several studies have reported tooth size variation between and within different racial groups. In order to improve the quality of dental care available, there is a great need for data on the mesiodistal crown dimensions of the individual teeth of Bangladeshi population. Objectives: To find nominative data on the mesiodistal crown dimensions of permanent teeth in Bangladeshi population and to compare the findings with those reported in other populations. Methods: This observational study was done from January, 2008 to June, 2010 in the Department of Orthodontics, Faculty of Dentistry, Bangabandhu Sheikh Mujib Medical University. A total of 244 Bangladeshi subjects (77 males and 167 females, aged 7 – 36 years (mean 18.3 years with no age limit who attended at the above mentioned place for treatment were included in the study. Main outcome measure was mesiodistal crown dimension of each tooth class of permanent dentition. Mesiodistal crown dimensions were measured from dental casts of the permanent teeth. Results: Males had significantly larger teeth than females for maxillary central incisors (p < 0.05 and for the mandibular second premolars (p < 0.001. In both sexes, the maxillary lateral incisors showed the greatest variability [coefficient of variation (CV 10.7%] and the maxillary canines the least (CV 6.9% in mesiodistal crown dimension. Mandibular canines displayed greater sexual dimorphism in mesiodistal crown size than in any other tooth classes. Comparisons of the mesiodistal crown dimensions between population groups showed that Bangladeshis have tooth sizes close to those of North Indians, Icelanders and Jordanians but larger than those of North American Whites. Conclusions: From this study, a standard for the mesiodistal crown dimensions of permanent dentition of Bangladeshi males and females are obtained. Key Words: Crown dimension; Mesio

  4. Suitability of Secondary PEEK Telescopic Crowns on Zirconia Primary Crowns: The Influence of Fabrication Method and Taper.

    Science.gov (United States)

    Merk, Susanne; Wagner, Christina; Stock, Veronika; Eichberger, Marlis; Schmidlin, Patrick R; Roos, Malgorzata; Stawarczyk, Bogna

    2016-11-08

    This study investigates the retention load (RL) between ZrO₂ primary crowns and secondary polyetheretherketone (PEEK) crowns made by different fabrication methods with three different tapers. Standardized primary ZrO₂ crowns were fabricated with three different tapers: 0°, 1°, and 2° ( n = 10/group). Ten secondary crowns were fabricated (i) milled from breCam BioHPP blanks (PM); (ii) pressed from industrially fabricated PEEK pellets (PP) (BioHPP Pellet); or (iii) pressed from granular PEEK (PG) (BioHPP Granulat). One calibrated operator adjusted all crowns. In total, the RL of 90 secondary crowns were measured in pull-off tests at 50 mm/min, and each specimen was tested 20 times. Two- and one-way ANOVAs followed by a Scheffé's post-hoc test were used for data analysis ( p impact on the results. Within the 2° taper, the fabrication method had no influence on the RL. Within the PM group, the 2° taper showed significantly higher retention load compared with the 1° taper. The taper with 0° was in the same range value as the 1° and 2° tapers. No impact of the taper on the retention value was observed between the PP groups. Within the PG groups, the 0° taper presented significantly lower RL than the 1° taper, whereas the 2° taper showed no differences. The fabrication method of the secondary PEEK crowns and taper angles showed no consistent effect within all tested groups.

  5. Experimental investigation of the abrasive crown dynamics in orbital atherectomy.

    Science.gov (United States)

    Zheng, Yihao; Belmont, Barry; Shih, Albert J

    2016-07-01

    Orbital atherectomy is a catheter-based minimally invasive procedure to modify the plaque within atherosclerotic arteries using a diamond abrasive crown. This study was designed to investigate the crown motion and its corresponding contact force with the vessel. To this end, a transparent arterial tissue-mimicking phantom made of polyvinyl chloride was developed, a high-speed camera and image processing technique were utilized to visualize and quantitatively analyze the crown motion in the vessel phantom, and a piezoelectric dynamometer measured the forces on the phantom during the procedure. Observed under typical orbital atherectomy rotational speeds of 60,000, 90,000, and 120,000rpm in a 4.8mm caliber vessel phantom, the crown motion was a combination of high-frequency rotation at 1000, 1500, and 1660.4-1866.1Hz and low-frequency orbiting at 18, 38, and 40Hz, respectively. The measured forces were also composed of these high and low frequencies, matching well with the rotation of the eccentric crown and the associated orbital motion. The average peak force ranged from 0.1 to 0.4N at different rotational speeds. Copyright © 2016 IPEM. Published by Elsevier Ltd. All rights reserved.

  6. Application of terrestrial laser scanning for measuring tree crown structures

    International Nuclear Information System (INIS)

    Pretzsch, H.; Seifert, S.; Huang, P.

    2011-01-01

    This paper addresses the potential of terrestrial laser scanning (TLS) for describing and modelling of tree crown structure and dynamics. We first present a general approach for the metabolic and structural scaling of tree crowns. Out of this approach we emphasize those normalization and scaling parameters which become accessible by TLS. For example we show how the individual tree leaf area index, convex hull, and its space-filling by leaves can be extracted out of laser scan data. This contributes to a theoretical and empirical substantiation of crown structure models which were missing so far for e.g. quantification of structural and species diversity in forest stands, inventory of crown biomass, species detection by remote sensing, and understanding of self- and alien-thinning in pure and mixed stands. Up to now works on this topic delivered a rather scattered empirical knowledge mainly by single inventories of trees and stands. In contrast, we recommend to start with a model approach, and to complete existing data with repeated TLS inventories in order to come to a consistent and theoretically based model of tree crowns. (author) [de

  7. Direct composite restoration of permanent anterior teeth uncomplicated crown fractures

    Directory of Open Access Journals (Sweden)

    Ashley Evans Nicholas

    2018-01-01

    Full Text Available An uncomplicated crown fracture is a fracture that involves only the tooth enamel or the dentin and tooth enamel without any damage or exposure to the pulp. Crown fracture of the anterior teeth usually caused by traumatic forces such as falls, accidents, violence, or sports activities. Traumatic injuries of the oral region frequently involve the anterior teeth, especially maxillary incisors due to the anatomic factors which may affect the functional and aesthetical values of the teeth. The objective of this literature study was to know more about uncomplicated crown fracture of the anterior teeth and its restoration. This research was a literature study performed by researching, highlighting various interesting facts and compiling the relevant published journals. The most common and ideal direct restoration of the anterior teeth was the composite resin restoration. The anterior teeth restoration was considered to be a complex and challenging case to solves due to the fact that besides reconstructing the tooth and regaining the function, the aesthetical aspect was also becoming the main objectives. The permanent anterior teeth uncomplicated crown fracture was the most common case of tooth fractures which was mainly caused by traumatic injuries such as falls, accidents, excessive forces, violence, and also sports activities. Dental injuries of the anterior teeth also affected the aesthetical properties and the function of the tooth. Composite resin restoration was able to performed directly on the permanent anterior teeth uncomplicated crown fracture.

  8. Crown sealing and buckling instability during water entry of spheres

    KAUST Repository

    Marston, J. O.

    2016-04-05

    We present new observations from an experimental investigation of the classical problem of the crown splash and sealing phenomena observed during the impact of spheres onto quiescent liquid pools. In the experiments, a 6 m tall vacuum chamber was used to provide the required ambient conditions from atmospheric pressure down to of an atmosphere, whilst high-speed videography was exploited to focus primarily on the above-surface crown formation and ensuing dynamics, paying particular attention to the moments just prior to the surface seal. In doing so, we have observed a buckling-type azimuthal instability of the crown. This instability is characterised by vertical striations along the crown, between which thin films form that are more susceptible to the air flow and thus are drawn into the closing cavity, where they atomize to form a fine spray within the cavity. To elucidate to the primary mechanisms and forces at play, we varied the sphere diameter, liquid properties and ambient pressure. Furthermore, a comparison between the entry of room-temperature spheres, where the contact line pins around the equator, and Leidenfrost spheres (i.e. an immersed superheated sphere encompassed by a vapour layer), where there is no contact line, indicates that the buckling instability appears in all crown sealing events, but is intensified by the presence of a pinned contact line. © 2016 Cambridge University Press.

  9. Biology and control of the raspberry crown borer (Lepidoptera: Sesiidae).

    Science.gov (United States)

    McKern, Jacquelyn A; Johnson, Donn T; Lewis, Barbara A

    2007-04-01

    This study explored the biology of raspberry crown borer, Pennisetia marginata (Harris) (Lepidoptera: Sesiidae), in Arkansas and the optimum timing for insecticide and nematode applications. The duration of P. marginata's life cycle was observed to be 1 yr in Arkansas. Insecticide trials revealed that bifenthrin, chlorpyrifos, imidacloprid, metaflumizone, and metofluthrin efficacy were comparable with that of azinphosmethyl, the only labeled insecticide for P. marginata in brambles until 2005. Applications on 23 October 2003 for plots treated with bifenthrin, chlorpyrifos, and azinphosmethyl resulted in >88% reduction in larvae per crown. Applications on 3 November 2004 of metaflumizone, metofluthrin, and bifenthrin resulted in >89% reduction in larvae per crown. Applications on 7 April 2005 for metofluthrin, imidacloprid, bifenthrin, metaflumizone, and benzoylphenyl urea resulted in >64% reduction in the number of larvae per crown. Applications on 6 May 2004 did not reduce larval numbers. The optimum timing for treatments was found to be between October and early April, before the larvae tunneled into the crowns of plants. Applying bifenthrin with as little as 468 liters water/ha (50 gal/acre) was found to be as effective against larvae as higher volumes of spray. Nematode applications were less successful than insecticides. Nematode applications of Steinernemafeltiae, Steinernema carpocapsae, and Heterorhabditis bacteriophora reduced larvae counts per plant by 46, 53, and 33%, respectively.

  10. Wind Tunnel Experiments to Study Chaparral Crown Fires.

    Science.gov (United States)

    Cobian-Iñiguez, Jeanette; Aminfar, AmirHessam; Chong, Joey; Burke, Gloria; Zuniga, Albertina; Weise, David R; Princevac, Marko

    2017-11-14

    The present protocol presents a laboratory technique designed to study chaparral crown fire ignition and spread. Experiments were conducted in a low velocity fire wind tunnel where two distinct layers of fuel were constructed to represent surface and crown fuels in chaparral. Chamise, a common chaparral shrub, comprised the live crown layer. The dead fuel surface layer was constructed with excelsior (shredded wood). We developed a methodology to measure mass loss, temperature, and flame height for both fuel layers. Thermocouples placed in each layer estimated temperature. A video camera captured the visible flame. Post-processing of digital imagery yielded flame characteristics including height and flame tilt. A custom crown mass loss instrument developed in-house measured the evolution of the mass of the crown layer during the burn. Mass loss and temperature trends obtained using the technique matched theory and other empirical studies. In this study, we present detailed experimental procedures and information about the instrumentation used. The representative results for the fuel mass loss rate and temperature filed within the fuel bed are also included and discussed.

  11. Binding of carbon dioxide to metal macrocycles: Toward a mechanistic understanding of electrochemical and photochemical carbon dioxide reduction

    Energy Technology Data Exchange (ETDEWEB)

    Fujita, E.

    1993-01-01

    Efforts were made to find effective catalysts for photochemical and electrochemical reduction of CO[sub 2]. We are studying the factors controlling excited-state lifetimes, electron-transfer rates to mediators/catalysts, properties of reduced mediators, binding of small molecules to reduced mediators, and reactivity of the mediators to yield the desired products. This document describes some of the results of binding on CO[sub 2] to metal macrocycles. The electrocatalytic activity of cobalt macrocycle complexes in reduction of CO[sub 2] in CO[sub 2]-saturated water at the Hg electrode is being studied. We are ready to study the mechanism and kinetics of the photochemical CO[sub 2] reduction in order to design more efficient photo-energy conversion systems. 19 refs.

  12. Binding of carbon dioxide to metal macrocycles: Toward a mechanistic understanding of electrochemical and photochemical carbon dioxide reduction

    Energy Technology Data Exchange (ETDEWEB)

    Fujita, E.

    1993-07-01

    Efforts were made to find effective catalysts for photochemical and electrochemical reduction of CO{sub 2}. We are studying the factors controlling excited-state lifetimes, electron-transfer rates to mediators/catalysts, properties of reduced mediators, binding of small molecules to reduced mediators, and reactivity of the mediators to yield the desired products. This document describes some of the results of binding on CO{sub 2} to metal macrocycles. The electrocatalytic activity of cobalt macrocycle complexes in reduction of CO{sub 2} in CO{sub 2}-saturated water at the Hg electrode is being studied. We are ready to study the mechanism and kinetics of the photochemical CO{sub 2} reduction in order to design more efficient photo-energy conversion systems. 19 refs.

  13. Uniform versus asymmetric shading mediates crown recession in conifers.

    Directory of Open Access Journals (Sweden)

    Amanda L Schoonmaker

    Full Text Available In this study we explore the impact of asymmetrical vs. uniform crown shading on the mortality and growth of upper and lower branches within tree crowns, for two conifer species: shade intolerant lodgepole pine (Pinus contorta and shade tolerant white spruce (Picea glauca. We also explore xylem hydraulics, foliar nutrition, and carbohydrate status as drivers for growth and expansion of the lower and upper branches in various types of shading. This study was conducted over a two-year period across 10 regenerating forest sites dominated by lodgepole pine and white spruce, in the lower foothills of Alberta, Canada. Trees were assigned to one of four shading treatments: (1, complete uniform shading of the entire tree, (2 light asymmetric shading where the lower 1/4-1/3 of the tree crown was shaded, (3 heavy asymmetric shading as in (2 except with greater light reduction and (4 control in which no artificial shading occurred and most of the entire crown was exposed to full light. Asymmetrical shading of only the lower crown had a larger negative impact on the bud expansion and growth than did uniform shading, and the effect was stronger in pine relative to spruce. In addition, lower branches in pine also had lower carbon reserves, and reduced xylem-area specific conductivity compared to spruce. For both species, but particularly the pine, the needles of lower branches tended to store less C than upper branches in the asymmetric shade, which could suggest a movement of reserves away from the lower branches. The implications of these findings correspond with the inherent shade tolerance and self-pruning behavior of these conifers and supports a carbon based mechanism for branch mortality--mediated by an asymmetry in light exposure of the crown.

  14. Provisional crown failures in dental school predoctoral clinics.

    Science.gov (United States)

    Hyde, Jeffrey D; Bader, James A; Shugars, Daniel A

    2007-11-01

    Following a preliminary study indicating that at least 10 percent of single-unit crown temporary restorations failed in patients who received treatment by predoctoral students, a comprehensive examination of provisional crown failure was initiated to identify strategies to reduce the failure rate. For all provisionalized, natural tooth, single-unit crown preparations in University of North Carolina School of Dentistry predoctoral clinics for one year (N=1008), we noted tooth type, type of crown, student level, faculty coverage experience, treatment clinic, temporary material and luting agent, and retreatment (failure) of the provisional restoration. For failures, we also noted the stage of crown preparation at failure and the time since initial placement of the temporary. We analyzed these data using simple cross-tabs and logistic regression on need for retreatment (alpha =0.05). The failure rate was 18.75 percent (N=189). The median time to failure was twelve days; the 25(th) and 75(th) percentiles were six and twenty-six days. Significant risk factors, in order of odds ratio estimates, were molar tooth, second- or third-year student, and inexperienced faculty. Most provisional failures occurred during the final preparation phase of treatment. Provisional restoration failure is more frequent than was initially suspected from preliminary studies. Strategies for institutional intervention to reduce provisional restoration failure include greater attention to evaluating provisional crowns placed by inexperienced students (sophomores and juniors) and placing more emphasis on the retentiveness of provisional restorations reused following the final impression. Review of provisional evaluation procedures is also indicated for faculty who do not routinely supervise these procedures.

  15. Dinuclear Silver(I) and Copper(II) Complexes of Hexadentate Macrocyclic Ligands Containing p-Xylyl Spacers

    DEFF Research Database (Denmark)

    McKenzie, Christine J.; Nielsen, Lars Preuss; Søtofte, Inger

    1998-01-01

    The cyclocondensation of terephthalic aldehyde with N,N-bis(3-aminopropyl)-methylamine in the presence of silver(I) gives the dinuclear tetramine Schiff base macrocyclic complex, [Ag2L1](NO3)2 (L1=7,22-N,N'-dimethyl-3,7,11,18, 22,26-hexaazatricyclo[26.2.21.18.213.16]-tetratricosa-2,11,13,15,1 7...

  16. Tools for Chemical Biology: New Macrocyclic Compounds from Diversity-Oriented Synthesis and Toward Materials from Silver(I) Acetylides

    DEFF Research Database (Denmark)

    Madsen, Charlotte Marie

    Part I The formation of a library of diverse macrocyclic compounds with different functionalities and ring sizes in a few steps from two easily accessible α,ω-diol building blocks is presented. The building blocks are combined by esteriffcations in four different ways leading to the formation of ...... of uoro-iodoadamantanes. However, overall the results provide a good starting point for the synthesis of new triptycene and adamantane-containing molecules that can interact with carbon nanotubes....

  17. Green chemistry for preparation of oligopyrrole macrocycles precursors: Novel methodology for dipyrromethanes and tripyrromethanes synthesis in water

    Czech Academy of Sciences Publication Activity Database

    Král, Vladimír; Vašek, P.; Dolenský, B.

    2004-01-01

    Roč. 69, č. 5 (2004), s. 1126-1136 ISSN 0010-0765 R&D Projects: GA ČR GA203/02/0933; GA ČR GA203/02/0420; GA ČR GP203/03/D049 Grant - others:QLRT(XE) 2000-02360 Keywords : oligopyrrole macrocycles * porphyrins * calixpyrrols Subject RIV: CC - Organic Chemistry Impact factor: 1.062, year: 2004

  18. Modeling the spatial distribution of forest crown biomass and effects on fire behavior with FUEL3D and WFDS

    Science.gov (United States)

    Russell A. Parsons; William Mell; Peter McCauley

    2010-01-01

    Crown fire poses challenges to fire managers and can endanger fire fighters. Understanding of how fire interacts with tree crowns is essential to informed decisions about crown fire. Current operational crown fire predictions in the United States assume homogeneous crown fuels. While a new class of research fire models, which model fire behavior with computational...

  19. AB INITIO INVESTIGATION OF 12-CROWN-4 AND BENZO-12-CROWN-4 COMPLEXES WITH Li+, Na+, K+, Zn2+, Cd2+, AND Hg2+

    Directory of Open Access Journals (Sweden)

    Yahmin Yahmin

    2010-06-01

    Full Text Available The structure and binding energies of 12-crown-4 and benzo-12-crown-4 complexes with Li+, Na+, K+, Zn2+, Cd2+, and Hg2+were investigated with ab initio calculations using Hartree-Fock approximation and second-order perturbation theory. The basis set used in this study is lanl2mb. The structure optimization of cation-crown ether complexes was evaluated at HF/lanl2mb level of theory and interaction energy of the corresponding complexes was calculated at MP2/lanl2mb level of theory (MP2/lanl2mb//HF/lanl2mb. Interactions of the crown ethers and the cations were discussed in term of the structure parameter of crown ether. The binding energies of the complexes show that all complex formed from transition metal cations is more stable than the complexes formed from alkali metal cations.   Keywords: 12-crown-4, benzo-12-crown-4, alkali metals, transition metals

  20. CROWN: A service grid middleware with trust management mechanism

    Institute of Scientific and Technical Information of China (English)

    HUAI Jinpeng; HU Chunming; LI Jianxin; SUN Hailong; WO Tianyu

    2006-01-01

    Based on a proposed Web service-based grid architecture, a service grid middleware system called CROWN is designed in this paper. As the two kernel points of the middleware, the overlay-based distributed grid resource management mechanism is proposed, and the policy-based distributed access control mechanism with the capability of automatic negotiation of the access control policy and trust management and negotiation is also discussed in this paper. Experience of CROWN testbed deployment and application development shows that the middleware can support the typical scenarios such as computing-intensive applications, data-intensive applications and mass information processing applications.

  1. Investigation of the potential of silica-bonded macrocyclic ligands for separation of metal ions from nuclear waste

    International Nuclear Information System (INIS)

    Camaioni, D.M.; Colton, N.G.; Bruening, R.L.

    1992-01-01

    This report describes the testing of some novel separations materials known as SuperLig trademark materials for their ability to separate efficiently and selectively certain metal ions from a synthetic, nonradioactive nuclear waste solution. The materials, developed and patented by IBC Advanced Technologies, are highly selective macrocyclic ligands that have been covalently bonded to silica gel. The SuperLig trademark materials that were tested are: (1) SuperLig trademark 601 for barium (Ba 2+ ) and strontium (Sr 2+ ) separation, (2) SuperLig trademark 602 for cesium (Cs + ) and rubidium (Rb + ) separation, (3) SuperLig trademark 27 for palladium (Pd 2+ ) separation, and (4) SuperLig trademark II for silver (Ag + ) and ruthenium (Ru 3+ ) separation. Our observations show that the technology for separating metal ions using silica-bonded macrocycles is essentially sound and workable to varying degrees of success that mainly depend on the affinity of the macrocycle for the metal ion of interest. It is expected that ligands will be discovered or synthesized that are amenable to separating metal ions of interest using this technology. Certainly more development, testing, and evaluation is warranted. 3 figs., 11 tabs

  2. Dinuclear Silver(I) and Copper(II) Complexes of Hexadentate Macrocyclic Ligands Containing p-Xylyl Spacers

    DEFF Research Database (Denmark)

    McKenzie, Christine J.; Nielsen, Lars Preuss; Søtofte, Inger

    1998-01-01

    The cyclocondensation of terephthalic aldehyde with N,N-bis(3-aminopropyl)-methylamine in the presence of silver(I) gives the dinuclear tetramine Schiff base macrocyclic complex, [Ag2L1](NO3)2 (L1=7,22-N,N'-dimethyl-3,7,11,18, 22,26-hexaazatricyclo[26.2.21.18.213.16]-tetratricosa-2,11,13,15,1 7......,26,28,30,31,33-decaene). [Ag2L1](NO3)2 crystallizes in the monoclinic space group P21/c, with a=14.153(6), b=12.263(4), c=9.220(2) Å, beta=97.52(3) Å and Z=2. The silver ions are strongly coordinated at each end of the macrocycle by the two imine nitrogen atoms [2.177(3) and 2.182(3) Å] with close interatomic...... interactions to an oxygen atom of a nitrate ion and an amine nitrogen atom [2.580(2) and 2.690(2) Å]. The Ag...Ag distance is 6.892(3) Å. The free tetraimine macrocycle, L1, was obtained by treatment of [Ag2L1](NO3)2 with an excess of iodide, and the reduced derivative 7,22-N,N'-dimethyl-3...

  3. Spectroscopic and electrochemical investigation with coordination stabilities: Mononuclear manganese(II) complexes derived from different constituents macrocyclic ligands

    Science.gov (United States)

    Kumar, Rajiv; Chnadra, S.; Mishra, Parashuram

    2007-12-01

    Since the manganese(II) complexes are known as having a high degree of stability, some of them may be able to play a very important role in biosystems. We prepared manganese(II) complexes with different chromospheres containing macrocyclic ligands bearing N, S and O like functional donor atoms in order to obtain different models of compounds. So these new manganese(II) complexes were derived from macrocyclic ligands by chelating them with metal ions. Thus, two macrocyclic ligands, L 1: 2,4-diphenyl-1,5-diaza-8,12-dioxo-6,7:13,14-dibenzocyclo tetradeca-1,4-diene[N 2O 2]ane; L 2: 2,4,9,11-tetraphenyl-6,13-dimethyl-1,5,8,12-traazacyclotertr-adeca-1,4,8,11-tetraene[N 4]ane; and two more different form first one viz.—L 3: 1,7-diaza-4-monothia-10,14-dioxo-8,9:15,16-cyclohexadecane[N 2O 2S]ane and L 4: 4,13-diaoxa-1,7,10,16-hexazacyclooctadecane[N 4O 2]ane were prepared and their capacity to retain the manganese(II) ion in solid as well as aqueous solution was determined from various physiochemical techniques viz: characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic, ESR spectral studies and cyclic voltammetric measurements.

  4. Through-Space Paramagnetic NMR Effects in Host-Guest Complexes: Potential Ruthenium(III) Metallodrugs with Macrocyclic Carriers.

    Science.gov (United States)

    Chyba, Jan; Novák, Martin; Munzarová, Petra; Novotný, Jan; Marek, Radek

    2018-04-05

    The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na + [ trans-Ru III Cl 4 (DMSO)(L)] - (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbit[ n]uril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host-guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.

  5. Unsaturated macrocyclic dihydroxamic acid siderophores produced by Shewanella putrefaciens using precursor-directed biosynthesis.

    Science.gov (United States)

    Soe, Cho Z; Codd, Rachel

    2014-04-18

    To acquire iron essential for growth, the bacterium Shewanella putrefaciens produces the macrocyclic dihydroxamic acid putrebactin (pbH2; [M + H(+)](+), m/zcalc 373.2) as its native siderophore. The assembly of pbH2 requires endogenous 1,4-diaminobutane (DB), which is produced from the ornithine decarboxylase (ODC)-catalyzed decarboxylation of l-ornithine. In this work, levels of endogenous DB were attenuated in S. putrefaciens cultures by augmenting the medium with the ODC inhibitor 1,4-diamino-2-butanone (DBO). The presence in the medium of DBO together with alternative exogenous non-native diamine substrates, (15)N2-1,4-diaminobutane ((15)N2-DB) or 1,4-diamino-2(E)-butene (E-DBE), resulted in the respective biosynthesis of (15)N-labeled pbH2 ((15)N4-pbH2; [M + H(+)](+), m/zcalc 377.2, m/zobs 377.2) or the unsaturated pbH2 variant, named here: E,E-putrebactene (E,E-pbeH2; [M + H(+)](+), m/zcalc 369.2, m/zobs 369.2). In the latter system, remaining endogenous DB resulted in the parallel biosynthesis of the monounsaturated DB-E-DBE hybrid, E-putrebactene (E-pbxH2; [M + H(+)](+), m/zcalc 371.2, m/zobs 371.2). These are the first identified unsaturated macrocyclic dihydroxamic acid siderophores. LC-MS measurements showed 1:1 complexes formed between Fe(III) and pbH2 ([Fe(pb)](+); [M](+), m/zcalc 426.1, m/zobs 426.2), (15)N4-pbH2 ([Fe((15)N4-pb)](+); [M](+), m/zcalc 430.1, m/zobs 430.1), E,E-pbeH2 ([Fe(E,E-pbe)](+); [M](+), m/zcalc 422.1, m/zobs 422.0), or E-pbxH2 ([Fe(E-pbx)](+); [M](+), m/zcalc 424.1, m/zobs 424.2). The order of the gain in siderophore-mediated Fe(III) solubility, as defined by the difference in retention time between the free ligand and the Fe(III)-loaded complex, was pbH2 (ΔtR = 8.77 min) > E-pbxH2 (ΔtR = 6.95 min) > E,E-pbeH2 (ΔtR = 6.16 min), which suggests one possible reason why nature has selected for saturated rather than unsaturated siderophores as Fe(III) solubilization agents. The potential to conduct multiple types of ex situ chemical

  6. In vitro fracture resistance of three commercially available zirconia crowns for primary molars.

    Science.gov (United States)

    Townsend, Janice A; Knoell, Patrick; Yu, Qingzhao; Zhang, Jian-Feng; Wang, Yapin; Zhu, Han; Beattie, Sean; Xu, Xiaoming

    2014-01-01

    The purpose of this study was to measure the fracture resistance of primary mandibular first molar zirconia crowns from three different manufacturers-EZ Pedo (EZP), NuSmile (NSZ), and Kinder Krowns (KK)-and compare it with the thickness of the zirconia crowns and the measured fracture resistance of preveneered stainless steel crowns (SSCs). The thickness of 20 zirconia crowns from three manufacturers were measured. The mean force required to fracture the crowns was determined. Preveneered NuSmile (NSW) SSCs were tested as a control. EZP crowns were significantly thicker in three of the six measured locations. The force required to fracture the EZP crown was significantly higher than that required for NSZ and KK. There was a positive correlation between fracture resistance and crown thickness in the mesial, distal, mesioocclusal, and distoocclusal dimensions. None of the zirconia crowns proved to be as resistant to fracture as the preveneered SSCs. Statistically significant differences were found among the forces required to fracture zirconia crowns by three different manufacturers. The increase in force correlated with crown thickness. The forces required to fracture the preveneered stainless steel crowns were greater than the forces required to fracture all manufacturers' zirconia crowns.

  7. Uranyl(VI) and lanthanum(III) complexes with functionalized macrocyclic and macroacyclic Schiff bases

    International Nuclear Information System (INIS)

    Aguiari, A.; Brianese, N.; Tamburini, S.; Vigato, P.A.

    1995-01-01

    Acyclic Schiff bases have been prepared by [2 + 1] condensation of 2,6-diformyl-4-chlorophenol and H 2 NCH 2 [CH 2 XCH 2 ] n CH 2 NH 2 (n =3D 0 H 2 -I; X =3D NH, S, O n =3D 1 H 2 -II...H 2 -IV; X =3D 0 n =3D 2 H 2 -V; X =3D 0 n =3D 3 H 2 -VI). The related uranlyl(VI) and lanthanum (III) complexes have bee synthesized by reaction by reaction of the preformed ligands with the appropriate salt or by the template procedure, in the presence of base. No base was employed in the preparation of lanthanum (III) complexes, La(H 2 -II)(NO 3 ) 3 , La(H 2 -IV)(NO 3 ) 3 where the Schiff bases coordinate as neutral chelate ligands. These acyclic complexes have been used for further condensation, and symmetric and asymmetric cyclic complexes have been obtained by their reaction with the polyamines H 2 NCH 2 [CH 2 XCH 2 ]nCH 2 NH 2 or with 4,4'-diaminodibenzo -18-crown-6. By reaction with 4-aminobenzo-15-crown-5 or 2-amino-methyl-15-crown-5, the same acyclic complexes give rise to functionalized complexes bearing crown-ether moieties. Analogously, the acyclic ligand H 3 -IXX, prepared by condensation of 2,6 diformyl-4-chlorophenol and tris(aminoethyl)amine, forms mono and homodinuclear lanthanum (III) complexes, which may undergo further condensation when reacted with primary functionalized amines. (authors). 42 refs., 2 figs., 2 schemes, 1 tab

  8. Biomechanical Assessment of Motor Abilities in Male Handball Players During the Annual Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Sacewicz Tomasz

    2016-12-01

    Full Text Available Introduction. The aim of the study was to determine the torque of the knee extensors and flexors of the lead lower limb, the torque of the shoulder extensors and flexors of the dominant upper limb, and the torque generated by the muscles of the kinematic chain going from the trail lower limb to the hand of the dominant limb in male handball players during the annual training macrocycle. Changes in jump height and throwing velocity were also investigated. Material and methods. The study involved 13 handball players from a Polish second-league team. The measurements were performed four times: at the beginning of the preparation period, at the beginning of the season, at the end of the first part of the season, and at the end of the second part of the season. Torque was measured in isokinetic and isometric conditions. Jumping ability was tested using a piezoelectric platform, and throwing velocity was measured with a speed radar gun. Results. The study found statistically significant differences between the relative torque values of the knee extensors (p < 0.002 and flexors (p < 0.003 of the lead leg measured in isokinetic conditions between the first three measurements and the final one. Isokinetic measurement of the torque of the muscles of the kinematic chain going from the trail leg to the hand of the dominant arm decreased in a statistically significant way at the end of the season. As for the results of the measurement of the torque of the shoulder extensors and flexors in static conditions, no statistically significant differences were observed between the four measurements. However, statistically significant differences were noted in jumping ability and throwing velocity in the annual training macrocycle. Conclusions. The results of the study indicate that there is a need to perform regular assessments of players’ strength and jumping ability during the competition period. There is a need to modify the training methods used during the

  9. Management of crown-of-thorns sea star (

    NARCIS (Netherlands)

    Bos, A.R.; Gumanao, G.S.; Mueller, B.; Saceda-Cardoza, M.M.E.

    2013-01-01

    Removals of crown-of-thorns sea stars (Acanthaster planci L) are crucial initiatives in limiting the damage to coral reefs during outbreaks, but have often been unable to control the populations. We hypothesized that reef topography and exact timing of removals (before reproduction) determine their

  10. Chemical constituent analysis of the crown-of-thorns starfish ...

    African Journals Online (AJOL)

    Jane

    2011-10-12

    Oct 12, 2011 ... negative influence on the growth and the health of the mice. Based on these results, we ..... This work was supported by the National Key Technology ... anticoagulant factor from the spine venom of the crown-of-thorns starfish ...

  11. Effect of detachment time of pineapple ( Ananas comosus L .) crown ...

    African Journals Online (AJOL)

    A limiting factor to large scale production of pineapple is the scarcity of planting materials. The use of pineapple crown as a propagation material is common, but with no regard to length of time after detachment. A study was conducted in the late seasons of 2007 and 2008 at the Teaching and Research Farm Ekiti State ...

  12. Evaluation of sampling strategies to estimate crown biomass

    Directory of Open Access Journals (Sweden)

    Krishna P Poudel

    2015-01-01

    Full Text Available Background Depending on tree and site characteristics crown biomass accounts for a significant portion of the total aboveground biomass in the tree. Crown biomass estimation is useful for different purposes including evaluating the economic feasibility of crown utilization for energy production or forest products, fuel load assessments and fire management strategies, and wildfire modeling. However, crown biomass is difficult to predict because of the variability within and among species and sites. Thus the allometric equations used for predicting crown biomass should be based on data collected with precise and unbiased sampling strategies. In this study, we evaluate the performance different sampling strategies to estimate crown biomass and to evaluate the effect of sample size in estimating crown biomass. Methods Using data collected from 20 destructively sampled trees, we evaluated 11 different sampling strategies using six evaluation statistics: bias, relative bias, root mean square error (RMSE, relative RMSE, amount of biomass sampled, and relative biomass sampled. We also evaluated the performance of the selected sampling strategies when different numbers of branches (3, 6, 9, and 12 are selected from each tree. Tree specific log linear model with branch diameter and branch length as covariates was used to obtain individual branch biomass. Results Compared to all other methods stratified sampling with probability proportional to size estimation technique produced better results when three or six branches per tree were sampled. However, the systematic sampling with ratio estimation technique was the best when at least nine branches per tree were sampled. Under the stratified sampling strategy, selecting unequal number of branches per stratum produced approximately similar results to simple random sampling, but it further decreased RMSE when information on branch diameter is used in the design and estimation phases. Conclusions Use of

  13. In vitro evaluation of the marginal integrity of CAD/CAM interim crowns.

    Science.gov (United States)

    Kelvin Khng, Kwang Yong; Ettinger, Ronald L; Armstrong, Steven R; Lindquist, Terry; Gratton, David G; Qian, Fang

    2016-05-01

    The accuracy of interim crowns made with computer-aided design and computer-aided manufacturing (CAD/CAM) systems has not been well investigated. The purpose of this in vitro study was to evaluate the marginal integrity of interim crowns made by CAD/CAM compared with that of conventional polymethylmethacrylate (PMMA) crowns. A dentoform mandibular left second premolar was prepared for a ceramic crown and scanned for the fabrication of 60 stereolithical resin dies, half of which were scanned to fabricate 15 Telio CAD-CEREC and 15 Paradigm MZ100-E4D-E4D crowns. Fifteen Caulk and 15 Jet interim crowns were made on the remaining resin dies. All crowns were cemented with Tempgrip under a 17.8-N load, thermocycled for 1000 cycles, placed in 0.5% acid fuschin for 24 hours, and embedded in epoxy resin before sectioning from the mid-buccal to mid-lingual surface. The marginal discrepancy was measured using a traveling microscope, and dye penetration was measured as a percentage of the overall length under the crown. The mean vertical marginal discrepancy of the conventionally made interim crowns was greater than for the CAD/CAM crowns (P=.006), while no difference was found for the horizontal component (P=.276). The mean vertical marginal discrepancy at the facial surface of the Caulk crowns was significantly greater than that of the other 3 types of interim crowns (Pmargin, the mean horizontal component of the Telio crowns was significantly larger than that of the other 3 types, with no difference at the lingual margins (P=.150). The mean percentage dye penetration for the Paradigm MZ100-E4D crowns was significantly greater and for Jet crowns significantly smaller than for the other 3 crowns (Pmarginal discrepancies of the Jet interim crowns at the facial surface and with the horizontal marginal discrepancies of the Caulk interim crowns at the lingual surface (Pmarginal discrepancy was found with the interim crowns fabricated by CAD/CAM as compared with PMMA crowns

  14. Asymptomatic ''crowned dens'' calcification in CT images for the craniovertebral junction

    International Nuclear Information System (INIS)

    Kubota, Gen; Mori, Masataka; Fukushima, Tatsuro

    2007-01-01

    Calcification around the odontoid process suggests 'crowned dens' syndrome, when accompanied with acute occipital headache or neck pain and with inflammatory signs. We retrospectively searched for calcification around the odontoid process in routine CT images of 282 patients emcompassing the craniovertebral junction, and found 13 (4.6%) had 'crowned dens' calcifications with neither characteristic symptoms nor signs suggestive for crowned dens' syndrome. Females of older ages frequently showed asymptomatic crowned dens' calcifications. (author)

  15. Effects of crown release on growth and quality of even-aged red maple stands

    Science.gov (United States)

    Terry F. Strong; Audra E. Hubbell; Adam H. Weise; Gayne G. Erdmann

    2006-01-01

    The effects of six crown-release treatments on growth and bole quality of 54 dominant, codominant, and intermediate red maples (Acer rubrum L.) were examined in an even-aged stand in upper Michigan. Treatments included an unreleased control, a single-tree and a two-tree crown release, and a full crown-to-crown release of 5, 10, and 15ft. Twenty-two...

  16. Synthesis, characterization and biological activity of symmetric dinuclear complexes derived from a novel macrocyclic compartmental ligand

    Energy Technology Data Exchange (ETDEWEB)

    Mruthyunjayaswamy, B.H.M.; Ijare, Omkar B.; Jadegoud, Y. [Gulbarga University (India). Dept. of Chemistry]. E-mail: bhmmswamy53@rediffmail.com

    2005-07-15

    A phenol based novel macrocyclic binucleating compartmental ligand N,N-bis(2,6-diiminomethyl-4-methyl-1-hydroxyphenyl)malonoyldicarboxamide was prepared. The complexes were prepared by template method by reacting 2,6-diformyl-4-methylphenol, malonoyl dihydrazide and the metal chlorides of Cu(II), Ni(II), Co(II), Cd(II), Zn(II) and Hg(II) in methanol to get a series of dinuclear complexes. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, UV-Vis, ESR, NMR and FAB mass spectral data. The dinuclear nature of the complexes was confirmed on the basis of elemental analyses, magnetic susceptibility, ESR and FAB mass spectral data. The ligand as well as Cu(II), Ni(II), Co(II) and Zn(II) complexes were tested for their antibacterial and antifungal properties against Escherichia coli, Staphyloccocus aureus, Aspergillus niger and Fusarium oxysporum. Magnetic susceptibility measurements of Cu(II), Ni(II) and Co(II) complexes reveal that these complexes exhibit antiferromagnetic coupling behavior due to the presence of two metal ions in close proximity. FAB mass spectrum of the Cu(II) complex gave a clear evidence for the dinuclear nature. The ligand and the complexes were found to be less active against the tested bacteria, but the ligand alone was found active against the fungus Fusarium oxysporum. (author)

  17. An eighteen-membered macrocyclic ligand for actinium-225 targeted alpha therapy

    International Nuclear Information System (INIS)

    Thiele, Nikki A.; MacMillan, Samantha N.; Wilson, Justin J.; Rodriguez-Rodriguez, Cristina

    2017-01-01

    The 18-membered macrocycle H 2 macropa was investigated for 225 Ac chelation in targeted alpha therapy (TAT). Radiolabeling studies showed that macropa, at submicromolar concentration, complexed all 225 Ac (26 kBq) in 5 min at RT. [ 225 Ac(macropa)] + remained intact over 7 to 8 days when challenged with either excess La 3+ ions or human serum, and did not accumulate in any organ after 5 h in healthy mice. A bifunctional analogue, macropa-NCS, was conjugated to trastuzumab as well as to the prostate-specific membrane antigen-targeting compound RPS-070. Both constructs rapidly radiolabeled 225 Ac in just minutes at RT, and macropa-Tmab retained >99 % of its 225 Ac in human serum after 7 days. In LNCaP xenograft mice, 225 Ac-macropa-RPS-070 was selectively targeted to tumors and did not release free 225 Ac over 96 h. These findings establish macropa to be a highly promising ligand for 225 Ac chelation that will facilitate the clinical development of 225 Ac TAT for the treatment of soft-tissue metastases. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Grafted chromium 13-membered dioxo-macrocyclic complex into aminopropyl-based nanoporous SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Joharian, Monika; Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Muzart, Jacques [Institut de Chimie Moléculaire de Reims, CNRS-Université de Reims Champagne-Ardenne, BP 1039, 51687 Reims Cedex 2 (France); Fallah, Mahtab [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of)

    2013-07-15

    In a new approach, chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 after four step reactions by using coordinating ability of anchored amino functionalized SBA-15. After the termination of each step, the obtained product was characterized by FT-IR, low-angle X-ray diffraction (LA-XRD), N{sub 2} adsorption–desorption isotherms (Brunauer–Emmett–Teller (BET)–Barret–Joyner–Halenda (BJH)) and thermogravimetric analysis (TGA), and used as catalyst for the efficient and regioselective alcoholysis of styrene oxide to 2-alkoxy-1-phenylethanol product at ambient temperature. - Graphical abstract: Chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 using coordinating ability of anchored amino functionalized SBA-15. Preparation of the catalyst is depicted in Scheme 1. - Highlights: • Dioxo tetraazachromium macrocyclic complex grafted into the SBA-15-NH{sub 2} channels. • The bond is created by coordinating ability of anchored amino functionalized SBA-15. • The prepared nanocatalyst has superior activity in the alcoholysis of styrene oxide. • The catalyst is reusable at ambient temperature for the mentioned reaction.

  19. Synthesis and hydrogenation application of Pt-Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer

    Science.gov (United States)

    Jin, Zhijun; Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

    2017-12-01

    Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10-x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10-x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd-Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd-Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5).

  20. Tetraazacyclohexadeca Macrocyclic Ligand as a Neutral Carrier in a Cr Ion-selective Electrode

    Directory of Open Access Journals (Sweden)

    Puja Saxena

    2004-12-01

    Full Text Available Abstract: A polystyrene-based membrane of 2,10-dimethyl-4,12-diphenyl-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene macrocyclic ionophore was prepared and investigated as Cr(III-selective electrode. The best performance was observed with the membrane having the polystyrene-ligand-dibutylphthalate-sodiumtetraphenyl borate composition 1:4:1:1 with a Nernstian slope of 19.0 mV per decade of concentration between pH 3.0 and 6.5. This electrode has been found to be chemically inert and of adequate stability with a response time of 20 s and was used over a period of 100 d with good reproducibility (S= 0.3 mV. The membrane works satisfactorily in a partially non-aqueous medium up to a maximum 30% (v/v content of methanol and ethanol. The potentiometric selectivity coefficient values indicate that the membrane sensor is highly selective for Cr(III ions over a number of monovalent, divalent and trivalent cations. The membrane electrode has also been successfully used to determine Cr3+ in various food materials.

  1. Synthesis and hydrogenation application of Pt–Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer

    Science.gov (United States)

    Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

    2017-01-01

    Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10−x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10−x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd–Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd–Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5). PMID:29308263

  2. Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

    Science.gov (United States)

    Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

    2017-11-01

    Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

  3. An eighteen-membered macrocyclic ligand for actinium-225 targeted alpha therapy

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, Nikki A.; MacMillan, Samantha N.; Wilson, Justin J. [Cornell Univ., Ithaca, NY (United States). Chemistry and Chemical Biology; Brown, Victoria; Jermilova, Una; Ramogida, Caterina F.; Robertson, Andrew K.H.; Schaffer, Paul; Radchenko, Valery [TRIUMF, Vancouver, BC (Canada). Life Science Div.; Kelly, James M.; Amor-Coarasa, Alejandro; Nikolopoulou, Anastasia; Ponnala, Shashikanth; Williams, Clarence Jr.; Babich, John W. [Radiology, Weill Cornell Medicine, New York, NY (United States); Rodriguez-Rodriguez, Cristina [British Columbia Univ., Vancouver, BC (Canada). Dept. of Physics and Astronomy and Centre for Comparative Medicine

    2017-11-13

    The 18-membered macrocycle H{sub 2}macropa was investigated for {sup 225}Ac chelation in targeted alpha therapy (TAT). Radiolabeling studies showed that macropa, at submicromolar concentration, complexed all {sup 225}Ac (26 kBq) in 5 min at RT. [{sup 225}Ac(macropa)]{sup +} remained intact over 7 to 8 days when challenged with either excess La{sup 3+} ions or human serum, and did not accumulate in any organ after 5 h in healthy mice. A bifunctional analogue, macropa-NCS, was conjugated to trastuzumab as well as to the prostate-specific membrane antigen-targeting compound RPS-070. Both constructs rapidly radiolabeled {sup 225}Ac in just minutes at RT, and macropa-Tmab retained >99 % of its {sup 225}Ac in human serum after 7 days. In LNCaP xenograft mice, {sup 225}Ac-macropa-RPS-070 was selectively targeted to tumors and did not release free {sup 225}Ac over 96 h. These findings establish macropa to be a highly promising ligand for {sup 225}Ac chelation that will facilitate the clinical development of {sup 225}Ac TAT for the treatment of soft-tissue metastases. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Zn and Fe complexes containing a redox active macrocyclic biquinazoline ligand.

    Science.gov (United States)

    Banerjee, Priyabrata; Company, Anna; Weyhermüller, Thomas; Bill, Eckhard; Hess, Corinna R

    2009-04-06

    A series of iron and zinc complexes has been synthesized, coordinated by the macrocyclic biquinazoline ligand, 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2'-biquinazolino)-[15]-1,3,5,8,10,14-hexaene-1,3,7,9,11,14-N(6) (Mabiq). The Mabiq ligand consists of a bipyrimidine moiety and two dihydropyrrole units. The electronic structures of the metal-Mabiq complexes have been characterized using spectroscopic and density-functional theory (DFT) computational methods. The parent zinc complex exhibits a ligand-centered reduction to generate the metal-coordinated Mabiq radical dianion, establishing the redox non-innocence of this ligand. Iron-Mabiq complexes have been isolated in three oxidation states. This redox series includes low-spin ferric and low-spin ferrous species, as well as an intermediate-spin Fe(II) compound. In the latter complex, the iron ion is antiferromagnetically coupled to a Mabiq-centered pi-radical. The results demonstrate the rich redox chemistry and electronic properties of metal complexes coordinated by the Mabiq ligand.

  5. Enantioseparation and chiral recognition mechanism of new chiral derivatives of xanthones on macrocyclic antibiotic stationary phases.

    Science.gov (United States)

    Fernandes, Carla; Tiritan, Maria Elizabeth; Cass, Quezia; Kairys, Visvaldas; Fernandes, Miguel Xavier; Pinto, Madalena

    2012-06-08

    A chiral HPLC method using four macrocyclic antibiotic chiral stationary phases (CSPs) has been investigated for determination of the enantiomeric purity of fourteen new chiral derivatives of xanthones (CDXs). The separations were performed with the CSPs Chirobiotic T, Chirobiotic TAG, Chirobiotic V and Chirobiotic R under multimodal elution conditions (normal-phase, reversed-phase and polar ionic mode). The analyses were performed at room temperature in isocratic mode and UV and CD detection at a wavelength of 254 nm. The best enantioselectivity and resolution were achieved on Chirobiotic R and Chirobiotic T CSPs, under normal elution conditions, with R(S) ranging from 1.25 to 2.50 and from 0.78 to 2.06, respectively. The optimized chromatographic conditions allowed the determination of the enantiomeric ratio of eight CDXs, always higher than 99%. In order to better understand the chromatographic behavior at a molecular level, and the structural features associated with the chiral recognition mechanism, computational studies by molecular docking were carried out using VDock. These studies shed light on the mechanisms involved in the enantioseparation for this important class of chiral compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Synthesis, characterization and biological activity of symmetric dinuclear complexes derived from a novel macrocyclic compartmental ligand

    International Nuclear Information System (INIS)

    Mruthyunjayaswamy, B.H.M.; Ijare, Omkar B.; Jadegoud, Y.

    2005-01-01

    A phenol based novel macrocyclic binucleating compartmental ligand N,N-bis(2,6-diiminomethyl-4-methyl-1-hydroxyphenyl)malonoyldicarboxamide was prepared. The complexes were prepared by template method by reacting 2,6-diformyl-4-methylphenol, malonoyl dihydrazide and the metal chlorides of Cu(II), Ni(II), Co(II), Cd(II), Zn(II) and Hg(II) in methanol to get a series of dinuclear complexes. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, UV-Vis, ESR, NMR and FAB mass spectral data. The dinuclear nature of the complexes was confirmed on the basis of elemental analyses, magnetic susceptibility, ESR and FAB mass spectral data. The ligand as well as Cu(II), Ni(II), Co(II) and Zn(II) complexes were tested for their antibacterial and antifungal properties against Escherichia coli, Staphyloccocus aureus, Aspergillus niger and Fusarium oxysporum. Magnetic susceptibility measurements of Cu(II), Ni(II) and Co(II) complexes reveal that these complexes exhibit antiferromagnetic coupling behavior due to the presence of two metal ions in close proximity. FAB mass spectrum of the Cu(II) complex gave a clear evidence for the dinuclear nature. The ligand and the complexes were found to be less active against the tested bacteria, but the ligand alone was found active against the fungus Fusarium oxysporum. (author)

  7. Tree crown structure indicators in a natural uneven-aged mixed coniferous forest in northeastern Mexico

    Science.gov (United States)

    Javier Jimenez-Perez; Oscar Aguirre-Calderon; Horst Kramer

    2006-01-01

    Characterization of tree crown structure provides critical information to assess a variety of ecological conditions for multiple purposes and applications. For biomass growth, for example, tree crowns have basic physiological functions: assimilation, respiration, and transpiration. How tree crowns spatially interact and grow can bring about a seamless landscape of...

  8. 78 FR 63559 - Order of Suspension of Trading; In The Matter of Crown Alliance Capital Limited

    Science.gov (United States)

    2013-10-24

    ... Alliance Capital Limited (``Crown Alliance''), quoted under the ticker symbol CACL, because of questions regarding the accuracy of assertions in Crown Alliance's public filings concerning the company's assets and... of Crown Alliance Capital Limited October 22, 2013. It appears to the Securities and Exchange...

  9. Comparison of Primary Molar Crown Dimensions with Stainless Steel Crowns in a Sample of Iranian Children

    Directory of Open Access Journals (Sweden)

    Hossein Afshar

    2015-06-01

    Full Text Available Background and aims. Due to anatomic variation in tooth anatomy between populations, this study compared the buccolingual (BL and mesiodistal (MD dimensions of primary molars with those of stainless steel crowns (SSCs in anIranian population. Materials and methods. Impressions were taken from both dental arches of children, and casts were poured. Teeth with caries, restoration, hypoplasia or other dental anomalies were excluded. 216 primary molars were selected and divided into 4 groups of 54 each (maxillary and mandibular first and second primary molars. MD/BL dimensions were measured using a digital caliper with 0.01 mm precision on casts and SCCs (3M brand. Data were assessed using paired t-test, post hoc test and ANOVA. P < 0.05 was considered statistically significant. Results. The MD dimension of the lower first molar SSC and the BL dimension of the lower second molar SSC had the least difference with the corresponding values of the respective teeth. The MD dimension of the upper second molar SSC and the BL dimension of the upper first molar SSC had the greatest difference with the corresponding values in the respective teeth. Comparison of the two different brands of SSCs for the upper first molar revealed that both types had significant differences with the teeth in terms of both MD (P = 0.0 and BL (P = 0.0 dimensions. Conclusion. In the studied population, best adaptation was seen in second lower molars and the least adaptationswere seen in first and second upper molars.

  10. Randomized, Controlled Clinical Trial of Bilayer Ceramic and Metal-Ceramic Crown Performance

    Science.gov (United States)

    Esquivel-Upshaw, Josephine; Rose, William; Oliveira, Erica; Yang, Mark; Clark, Arthur E.; Anusavice, Kenneth

    2013-01-01

    Purpose Analyzing the clinical performance of restorative materials is important, as there is an expectation that these materials and procedures will restore teeth and do no harm. The objective of this research study was to characterize the clinical performance of metal-ceramic crowns, core ceramic crowns, and core ceramic/veneer ceramic crowns based on 11 clinical criteria. Materials and Methods An IRB-approved, randomized, controlled clinical trial was conducted as a single-blind pilot study. The following three types of full crowns were fabricated: (1) metal-ceramic crown (MC) made from a Pd-Au-Ag-Sn-In alloy (Argedent 62) and a glass-ceramic veneer (IPS d.SIGN veneer); (2) non-veneered (glazed) lithium disilicate glass-ceramic crown (LDC) (IPS e.max Press core and e.max Ceram Glaze); and (3) veneered lithia disilicate glass-ceramic crown (LDC/V) with glass-ceramic veneer (IPS Empress 2 core and IPS Eris). Single-unit crowns were randomly assigned. Patients were recalled for each of 3 years and were evaluated by two calibrated clinicians. Thirty-six crowns were placed in 31 patients. A total of 12 crowns of each of the three crown types were studied. Eleven criteria were evaluated: tissue health, marginal integrity, secondary caries, proximal contact, anatomic contour, occlusion, surface texture, cracks/chips (fractures), color match, tooth sensitivity, and wear (of crowns and opposing enamel). Numerical rankings ranged from 1 to 4, with 4 being excellent, and 1 indicating a need for immediate replacement. Statistical analysis of the numerical rankings was performed using a Fisher’s exact test. Results There was no statistically significant difference between performance of the core ceramic crowns and the two veneered crowns at year 1 and year 2 (p > 0.05). All crowns were rated either as excellent or good for each of the clinical criteria; however, between years 2 and 3, gradual roughening of the occlusal surface occurred in some of the ceramic-ceramic crowns

  11. PEEK Primary Crowns with Cobalt-Chromium, Zirconia and Galvanic Secondary Crowns with Different Tapers—A Comparison of Retention Forces

    Directory of Open Access Journals (Sweden)

    Veronika Stock

    2016-03-01

    Full Text Available In prosthetic dentistry, double crown systems have proved their suitability as retainers for removable partial dentures. However, investigations in this context, regarding polyetheretherketone, are scarce. Therefore, the aim of this study was to test the retention force (RF between polyetheretherketone (PEEK primary and cobalt-chromium (CoCr, zirconia (ZrO2 and galvanic (GAL secondary crowns with three different tapers. Primary PEEK-crowns were milled with the tapers 0°, 1°, and 2° (n = 10/taper, respectively. Afterwards, 90 secondary crowns were fabricated: (i 30 CoCr-crowns milled from Ceramill Sintron (AmannGirrbach, Koblach, Austria (n = 10/taper, (ii 30 ZrO2-crowns milled from Ceramill ZI (AmannGirrbach, Koblach, Austria (n = 10/taper, and (iii 30 GAL-crowns made using electroforming (n = 10/taper. RF was measured in a pull-off test (20 pull-offs/specimen and data were analyzed using 2-/1-way Analysis of Variance (ANOVA followed by the Tukey-Honestly Significant Difference (HSD post hoc test and linear regression analyses (p < 0.05. The measured mean RF values ranged between 9.6 and 38.2 N. With regard to the 0°, 1°, and 2° tapered crowns, no statistically significant differences between CoCr and ZrO2 were observed (p > 0.141. At 0° taper, no differences in retention forces between GAL, CrCr, and ZrO2 crowns were found (p = 0.075. However, at 1° and 2° taper, lower RF for GAL-crowns were observed (p < 0.009, p < 0.001, respectively. According to this laboratory study, PEEK might be a suitable material for primary crowns, regardless of the taper and the material of secondary crown. Long-term results, however, are still necessary.

  12. “One Ring to Bind Them All”—Part I: The Efficiency of the Macrocyclic Scaffold for G-Quadruplex DNA Recognition

    Directory of Open Access Journals (Sweden)

    David Monchaud

    2010-01-01

    Full Text Available Macrocyclic scaffolds are particularly attractive for designing selective G-quadruplex ligands essentially because, on one hand, they show a poor affinity for the “standard” B-DNA conformation and, on the other hand, they fit nicely with the external G-quartets of quadruplexes. Stimulated by the pioneering studies on the cationic porphyrin TMPyP4 and the natural product telomestatin, follow-up studies have developed, rapidly leading to a large diversity of macrocyclic structures with remarkable-quadruplex binding properties and biological activities. In this review we summarize the current state of the art in detailing the three main categories of quadruplex-binding macrocycles described so far (telomestatin-like polyheteroarenes, porphyrins and derivatives, polyammonium cyclophanes, and in addressing both synthetic issues and biological aspects.

  13. A comparative study of the structure and luminescence of mono- and dinuclear crown-ether lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Keyla M.N. de [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Batista, Hélcio J., E-mail: helciojb@gmail.com [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Belian, Mônica F. [Departamento de Química, Universidade Federal Rural de Pernambuco, Rua Dom Manoel de Medeiros, S/N – Dois Irmãos, 52171-900 Recife, Pernambuco (Brazil); Silva, Wagner E. [Unidade Acadêmica do Cabo de Santo Agostinho, Universidade Federal Rural de Pernambuco, 54510-000 Cabo de Santo Agostinho, Pernambuco (Brazil); Silva, Juliana A.B. da [Centro Acadêmico do Agreste, Universidade Federal de Pernambuco, 55002-970 Caruaru, Pernambuco (Brazil)

    2016-02-15

    Using as precursor the mononuclear lanthanide (Ln) macrocyclic complex, based on the 15-crown-5 ether (C) ligand and coordinated water (W) molecules, [LnCW{sub 4}]{sup 3+}, four novel analogous complexes for each of the three Ln(III) ions (Ln=Eu, Tb and Gd) were synthesized through systematic substitution of water molecules by the antenna-type ligands: 2,2′-dipyridyl (D), 1,10-phenanthroline (P) and 2,2′;6',2′′-terpyridine (T). The corresponding formulae of the complexes, obtained in a trichloride salt form, were the following: [LnCW{sub 4}]{sup 3+}, [LnCP{sub 2}]{sup 3+}, [LnCDW]{sup 3+}, [LnCDP]{sup 3+}, and [LnCT]{sup 3+}. The compounds were characterized by elemental analysis, UV and infrared spectroscopy and investigated through luminescence spectroscopy. For the Eu(III) and Tb(III) complex series, the most luminescent ones were [EuCDP]{sup 3+} and [TbCT]{sup 3+}, respectively. Motivated by this fact, two dinuclear analogous Eu(III) and Tb(III) complexes, based on the two-site coordinating macrocyclic ligand lariat-silacrown ether (S), as well as analogous Gd(III) complexes, were obtained as hexachloride salts with the following formulae: [Eu{sub 2}SD{sub 2}P{sub 2}]{sup 6+}, [Gd{sub 2}SD{sub 2}P{sub 2}]{sup 6+}, [Tb{sub 2}ST{sub 2}]{sup 6+} and [Gd{sub 2}ST{sub 2}]{sup 6+}. Also, [Eu{sub 2}SW{sub 8}]{sup 6+}, [Tb{sub 2}SW{sub 8}]{sup 6+} and [Gd{sub 2}SW{sub 8}]{sup 6+} complexes were prepared and used as reference non-antenna type dinuclear compounds. Comparing the luminescence between the antenna mononuclear complexes with the analogous dinuclear ones, for Eu(III) and Tb(III) ions, almost no change was observed. On the other hand, in the particular case of Eu(III), comparing the mono- and dinuclear non-antenna reference complexes [EuCW{sub 4}]{sup 3+} and [Eu{sub 2}SW{sub 8}]{sup 6+}, a surprisingly much higher luminescence intensity was observed for the dinuclear complex (~ one order of magnitude). The proposed cause for this behavior is the

  14. Failure analysis of various monolithic posterior aesthetic dental crowns using finite element method

    Science.gov (United States)

    Porojan, Liliana; Topală, Florin

    2017-08-01

    The aim of the study was to assess the effect of material stiffness and load on the biomechanical performance of the monolithic full-coverage posterior aesthetic dental crowns using finite element analysis. Three restorative materials for monolithic dental crowns were selected for the study: zirconia; lithium disilicate glass-ceramic, and resin-based composite. Stresses were calculated in the crowns for all materials and in the teeth structures, under different load values. The experiments show that dental crowns made from all this new aesthetic materials processed by CAD/CAM technologies would be indicated as monolithic dental crowns for posterior areas.

  15. Design algorithm for generatrix profile of cylindrical crowned rollers

    Directory of Open Access Journals (Sweden)

    Creţu Spiridon

    2017-01-01

    Full Text Available The cross-section of roller profile controls the pressure distribution in the contact area and radically affects the roller bearings basic dynamic load rating and rating lives. Today the most used roller profiles are the logarithmic profile and cylindrical-crowned (ZB profile. The logarithmic profile has a continuous evolution with no discontinuities till the intersection with the end fillet while ZB profile has two more discontinuities at the intersections points between the crowning circle and straight line generatrix. Using a semianalytical method, a numerical study has been carried out to find the optimum ZB profile for rollers incorporated in cylindrical rollers bearings. The basic reference rating life (L10_r has been used as optimization criterion.

  16. 18F-fluorination by crown ether-metal fluoride

    International Nuclear Information System (INIS)

    Irie, T.; Fukushi, K.; Ido, T.; Kasida, Y.; Nozaki, T.

    1982-01-01

    18 F-Fluorination by ''naked'' 18 F - anion produced by complexing anhydrous K 18 F, which was prepared from aqueous 18 F, with 18 -Crown-6 was described for preparing 18 F-21-fluoroprogesterone. In order to find out optimum conditions in this labelling method, various factors were investigated such as the solubility of KF in organic solvents containing 18 -Crown-6 and its reactivity for the nucleophilic displacement of 21-mesylate of progesterone. Chloroform was a good solvent in solubilization of KF and its reactivity. Problems in this labelling procedure were also examined, such as a supporter for transferring the labelled anhydrous K 18 F and reaction vessels. Use of a Teflon reaction vessel resulted in a good radiochemical yield based on the starting activity of $ 18 water. (author)

  17. 18F-fluorination by crown ether-metal fluoride

    International Nuclear Information System (INIS)

    Irie, T.; Fukushi, K.; Ido, T.; Kasida, Y.; Nozaki, T.

    1984-01-01

    For non-carrier-added 18 F-labeling of organic compounds, details were studied concerning the previously developed KF-crown ether method. In the modified method, a minute amount of KOH instead of carrier KF is added for the preparation of the anhydrous 18 F from aqueous carrier-free 18 F. The following factors were examined in order to determine optimum conditions for the preparation of the anhydrous non-carrier-added 18 F and the labeling synthesis with it: effects of the vessel on the evaporation of the 18 F-KOH solution and the amount of added KOH for the conversion of aqueous 18 F to anhydrous 18 F, the solubilized activity of the 18 F obtained by the evaporation in organic solutions containing 18-Crown-6 and the labeling reaction, as exemplified by the synthesis of 21-fluoroprogesterone. (author)

  18. Increasing the thermopower of crown-ether-bridged anthraquinones

    Science.gov (United States)

    Ismael, Ali K.; Grace, Iain; Lambert, Colin J.

    2015-10-01

    We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The thermopowers of both 1 and 2 are negative and at room temperature are optimised by binding with TTF alone, achieving thermpowers of -600 μV K-1 and -285 μV K-1 respectively. At much lower temperatures, which are relevant to cascade coolers, we find that for 1, a combination of TTF and Na+ yields a maximum thermopower of -710 μV K-1 at 70 K, whereas a combination of TTF and Li+ yields a maximum thermopower of -600 μV K-1 at 90 K. For 2, we find that TTF doping yields a maximum thermopower of -800 μV K-1 at 90 K, whereas at 50 K, the largest thermopower (of -600 μV K-1) is obtain by a combination TTF and K+ doping. At room temperature, we obtain power factors of 73 μW m-1 K-2 for 1 (in combination with TTF and Na+) and 90 μW m-1 K-2 for 2 (with TTF). These are higher or comparable with reported power factors of other organic materials.We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The

  19. Reduction of HCCI combustion noise through piston crown design

    DEFF Research Database (Denmark)

    Pedersen, Troels Dyhr; Schramm, Jesper

    2010-01-01

    . The largest and most consistent reduction in noise level was however achieved with a diesel bowl type piston. The increased surface area as well as the larger crevice volumes of the experimental piston crowns generally resulted in lower IMEP than the flat piston. While the crevice volumes can be reduced...... away from the engine. The experiments were conducted in a diesel engine that was run in HCCI combustion mode with a fixed quantity of DME as fuel. The results show that combustion knock is effectively suppressed by limiting the size of the volume in which the combustion occurs. Splitting...... the compression volume into four smaller volumes placed between the perimeter of the piston and the cylinder liner increased the noise to a higher level than that generated with a flat piston crown. This was due to resonance between the four volumes. Using eight volumes instead decreased the noise. The noise...

  20. Modeling tree crown dynamics with 3D partial differential equations.

    Science.gov (United States)

    Beyer, Robert; Letort, Véronique; Cournède, Paul-Henry

    2014-01-01

    We characterize a tree's spatial foliage distribution by the local leaf area density. Considering this spatially continuous variable allows to describe the spatiotemporal evolution of the tree crown by means of 3D partial differential equations. These offer a framework to rigorously take locally and adaptively acting effects into account, notably the growth toward light. Biomass production through photosynthesis and the allocation to foliage and wood are readily included in this model framework. The system of equations stands out due to its inherent dynamic property of self-organization and spontaneous adaptation, generating complex behavior from even only a few parameters. The density-based approach yields spatially structured tree crowns without relying on detailed geometry. We present the methodological fundamentals of such a modeling approach and discuss further prospects and applications.

  1. Thermodynamic studies of the complexation of plutonium(IV) by linear and macrocyclic poly-amino-carboxylate ligands

    International Nuclear Information System (INIS)

    Burgat, Romain

    2007-01-01

    In the framework of a collaboration between the CEA (Commissariat a l Energie Atomique) of Valduc and the ICMUB (Institut de Chimie Moleculaire de l Universite de Bourgogne), a study platform of the structural and physico-chemical properties of the radioelements U, Pu and Am complexes has been implemented. The plutonium(IV) complexation has been studied in a molar nitrate medium. The affinity of three linear poly-amino-carboxylates (EDTA, CDTA and DTPA) towards plutonium(IV) has then been estimated. For the three ligands, the formation constants of the monoleptic complexes Pu(EDTA), Pu(CDTA) and [Pu(DTPA)] - have been determined in a (H,K)NO 3 1 M medium and then extrapolated at a zero ionic force with the specific interactions theory (SIT). For the three complexes, mono-hydroxylated monoleptic species have been observed. With the EDTA and the CDTA, protonated dileptic complexes of a general formula [Pu(L) 2 H h ] (4-h)- have been revealed too. Nevertheless, the steric hindrance around the metallic center is too important to allow to a second molecule of DTPA to coordinate the Pu 4+ cation. The exclusive formation of the species [Pu(DTPA)] - and [Pu(DTPA)(OH)] 2- has been confirmed by capillary electrophoresis (EC-ICP-MS). On account of the preliminary results obtained during the titration of the cyclame tetraacetic product (TETRA) in presence of plutonium(IV), the adding of a competitive ligand such as EDTA has been considered for the study of the complexation of this radioelement by macrocyclic ligands. At last, the affinity of different macrocyclic ligands containing either four amide functions (TETAMMe 2 and TETAMMEt 2 ) or carboxylate groups (TETA, DOTPr and TETPr) towards lanthanides(III) has been estimated too. Although the complexation reaction be fast with the two first ligands, these complexes are less stable than those formed with the carboxylic macrocycles. (O.M.)

  2. Canopy Fuel Load Mapping of Mediterranean Pine Sites Based on Individual Tree-Crown Delineation

    Directory of Open Access Journals (Sweden)

    Giorgos Mallinis

    2013-12-01

    Full Text Available This study presents an individual tree-crown-based approach for canopy fuel load estimation and mapping in two Mediterranean pine stands. Based on destructive sampling, an allometric equation was developed for the estimation of crown fuel weight considering only pine crown width, a tree characteristic that can be estimated from passive imagery. Two high resolution images were used originally for discriminating Aleppo and Calabrian pines crown regions through a geographic object based image analysis approach. Subsequently, the crown region images were segmented using a watershed segmentation algorithm and crown width was extracted. The overall accuracy of the tree crown isolation expressed through a perfect match between the reference and the delineated crowns was 34.00% for the Kassandra site and 48.11% for the Thessaloniki site, while the coefficient of determination between the ground measured and the satellite extracted crown width was 0.5. Canopy fuel load values estimated in the current study presented mean values from 1.29 ± 0.6 to 1.65 ± 0.7 kg/m2 similar to other conifers worldwide. Despite the modest accuracies attained in this first study of individual tree crown fuel load mapping, the combination of the allometric equations with satellite-based extracted crown width information, can contribute to the spatially explicit mapping of canopy fuel load in Mediterranean areas. These maps can be used among others in fire behavior prediction, in fuel reduction treatments prioritization and during active fire suppression.

  3. The marginal fit of selective laser melting-fabricated metal crowns: an in vitro study.

    Science.gov (United States)

    Xu, Dan; Xiang, Nan; Wei, Bin

    2014-12-01

    The selective laser melting technique is attracting interest in prosthetic dentistry. The marginal fit is a key criterion for fixed restorations. The purpose of the study was to evaluate the marginal fit of cast cobalt-chromium alloy crowns versus the fit of selective laser melting-fabricated crowns. The marginal gap widths of 36 single crowns (18 selective laser melting-fabricated cobalt-chromium metal crowns and 18 cobalt-chromium cast crowns) were determined with a silicone replica technique. Each crown specimen was cut into 4 sections, and the marginal gap width of each cross section was evaluated by stereomicroscopy (× 100). The Student t test was used to evaluate whether significant differences occurred in the marginal gap widths between the selective laser melting-fabricated and cast cobalt-chromium metal crowns (α=.05). The mean marginal gap width of the cast crowns (170.19 μm) was significantly wider than that of the selective laser melting-fabricated crowns (102.86 μm). Selective laser melting-fabricate cobalt-chromium dental crowns found improved marginal gap widths compared with traditional cast crowns. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  4. Marginal Fit of CEREC Crowns at Different Finish Line Curvatures

    Science.gov (United States)

    2015-06-01

    the percolation of bacteria. Micro-leakage in the oral cavity can cause inflammation of the vital pulp and caries. Poor marginal adaptation of...exhibit physiologically age-related gingival recession; similarly, patients with a history of periodontal disease may have pathologic gingival...Mikroleakage - ful crowns and the dental pulp . Journal of Endodontics, 18, 473. Grey, N., Piddock, V., & Wilson, M. {1993). In vitro comparison of

  5. PROGRAM HTVOL: The Determination of Tree Crown Volume by Layers

    Science.gov (United States)

    Joseph C. Mawson; Jack Ward Thomas; Richard M. DeGraaf

    1976-01-01

    A FORTRAN IV computer program calculates, from a few field measurements, the volume of tree crowns. This volume is in layers of a specified thickness of trees or large shrubs. Each tree is assigned one of 15 solid forms, formed by using one of five side shapes (a circle, an ellipse, a neiloid, a triangle, or a parabolalike shape), and one of three bottom shapes (a...

  6. How resilient are southwestern ponderosa pine forests after crown fires?

    OpenAIRE

    Savage, M; Mast, J N

    2005-01-01

    The exclusion of low-severity surface fire from ponderosa pine (Pinus ponderosa P. & C. Lawson) forests of the Southwest has changed ecosystem structure and function such that severe crown fires are increasingly causing extensive stand mortality. This altered fire regime has resulted from the intersection of natural drought cycles with human activities that have suppressed natural fires for over a century. What is the trajectory of forest recovery after such fires? This study explores the reg...

  7. Provisional Crown Dislodgement during Scuba Diving: A Case of Barotrauma

    OpenAIRE

    Gulve, Meenal Nitin; Gulve, Nitin Dilip

    2013-01-01

    Changes in ambient pressure, for example, during flying, diving, or hyperbaric oxygen therapy, can lead to barotrauma. Although it may seem that this issue was neglected in dental education and research in recent decades, familiarity with and understanding of these facts may be of importance for dental practitioners. We report the case of a patient who experienced barotrauma involving dislodgement of a provisional crown during scuba diving. Patients who are exposed to pressure changes as a pa...

  8. Laboratory fire behavior measurements of chaparral crown fire

    Science.gov (United States)

    C. Sanpakit; S. Omodan; D. Weise; M Princevac

    2015-01-01

    In 2013, there was an estimated 9,900 wildland fires that claimed more than 577,000 acres of land. That same year, about 542 prescribed fires were used to treat 48,554 acres by several agencies in California. Being able to understand fires using laboratory models can better prepare individuals to combat or use fires. Our research focused on chaparral crown fires....

  9. A short-term clinical evaluation of IPS Empress 2 crowns.

    Science.gov (United States)

    Toksavul, Suna; Toman, Muhittin

    2007-01-01

    The aim of this study was to evaluate the clinical performance of all-ceramic crowns made with the IPS Empress 2 system after an observation period of 12 to 60 months. Seventy-nine IPS Empress 2 crowns were placed in 21 patients. The all-ceramic crowns were evaluated clinically, radiographically, and using clinical photographs. The evaluations took place at baseline (2 days after cementation) and at 6-month intervals for 12 to 60 months. Survival rate of the crowns was determined using Kaplan-Meier statistical analysis. Based on the US Public Health Service criteria, 95.24% of the crowns were rated satisfactory after a mean follow-up period of 58 months. Fracture was registered in only 1 crown. One endodontically treated tooth failed as a result of fracture at the cervical margin area. In this in vivo study, IPS Empress 2 crowns exhibited a satisfactory clinical performance during an observation period ranging from 12 to 60 months.

  10. Plant responses to Agrobacterium tumefaciens and crown gall development

    Science.gov (United States)

    Gohlke, Jochen; Deeken, Rosalia

    2014-01-01

    Agrobacterium tumefaciens causes crown gall disease on various plant species by introducing its T-DNA into the genome. Therefore, Agrobacterium has been extensively studied both as a pathogen and an important biotechnological tool. The infection process involves the transfer of T-DNA and virulence proteins into the plant cell. At that time the gene expression patterns of host plants differ depending on the Agrobacterium strain, plant species and cell-type used. Later on, integration of the T-DNA into the plant host genome, expression of the encoded oncogenes, and increase in phytohormone levels induce a fundamental reprogramming of the transformed cells. This results in their proliferation and finally formation of plant tumors. The process of reprogramming is accompanied by altered gene expression, morphology and metabolism. In addition to changes in the transcriptome and metabolome, further genome-wide (“omic”) approaches have recently deepened our understanding of the genetic and epigenetic basis of crown gall tumor formation. This review summarizes the current knowledge about plant responses in the course of tumor development. Special emphasis is placed on the connection between epigenetic, transcriptomic, metabolomic, and morphological changes in the developing tumor. These changes not only result in abnormally proliferating host cells with a heterotrophic and transport-dependent metabolism, but also cause differentiation and serve as mechanisms to balance pathogen defense and adapt to abiotic stress conditions, thereby allowing the coexistence of the crown gall and host plant. PMID:24795740

  11. Surgical crown lengthening: a 12-month study - radiographic results

    Directory of Open Access Journals (Sweden)

    Daniela Eleutério Diniz

    2007-08-01

    Full Text Available OBJECTIVE: The purpose of this study was to perform a radiographic follow-up evaluation after a 12-month healing period, following crown lengthening surgery. MATERIAL AND METHODS: Twenty-three periodontally healthy subjects (mean age 32.5 years that required crown lengthening surgery in premolars were recruited. In a total of 30 premolars, full thickness flaps, osseous resection, and flap suturing were performed. The restorative margin was defined in the pre-surgical phase and maintained unaltered during the healing period, serving as a reference point. Standardized bitewing radiographs were taken before and after osseous reduction, and at 2, 3, 6, and 12-month healing periods. RESULTS: Intact lamina dura was observed at both mesial and distal alveolar crests only from the 3rd month. At 12-months, all alveolar crests presented lamina dura. The overall mean distance from the restorative margin to the alveolar crest achieved after osseous resection was 3.28±0.87 mm at mesial and 2.81±0.51 mm at distal sites. No significant radiographic changes in the bone crest were observed during a 12-month healing period. CONCLUSION: The findings of this study suggest that the radiographic proximal bone level observed on bitewing radiographs following crown lengthening surgery can be used as a reference to predict the future level of the healed alveolar crest.

  12. Macrocyclic trichothecenes are undetectable in kudzu (Pueraria montana) plants treated with a high-producing isolate of Myrothecium verrucaria.

    Science.gov (United States)

    Abbas, H K; Tak, H; Boyette, C D; Shier, W T; Jarvis, B B

    2001-09-01

    Myrothecium verrucaria was found to be an effective pathogen against kudzu grown in the greenhouse and the field. M. verrucaria produced large amounts of macrocyclic trichothecenes when cultured on solid rice medium, including epiroridin E (16.8 mg/g crude extract), epiisororidin E (1 mg/g), roridin E (8.7 mg/g), roridin H (31.3 mg/g), trichoverrin A (0.6 mg/g), trichoverrin B (0.1 mg/g), verrucarin A (37.4 mg/g), and verrucarin J (2.2 mg/g). Most of these toxins were also isolated from M. verrucaria spores and mycelia grown on potato dextrose agar medium, including epiroridin E (32.3 mg/g), epiisororidin E (28.6 mg/g), roridin E (0 mg/g), roridin H (60 mg/g), trichoverrin A (1.3 mg/g), trichoverrin B (1.8 mg/g), verrucarin A (13.8 mg/g), and verrucarin J (131 mg/g). When M. verrucaria was cultured on liquid media, the numbers but not the amounts of toxins decreased. Only epiroridin E (28.3 mg/g), epiisororidin E (29.6 mg/g), verrucarin B (195 mg/g) and verrucarin J (52.6 mg/g) were measured when the fungus was cultured on cornsteep medium. On soyflour-cornmeal broth M. verrucaria produced several toxins, including epiroridin E (58.1 mg/g), epiisororidin E (5.8 mg/g), verrucarin B (29.9 mg/g) and verrucarin J (32 mg/g). In contrast, no macrocyclic trichothecenes were detected by HPLC analysis of plant tissues of kudzu, sicklepod, and soybean treated with aqueous suspensions of M. verrucaria spores formulated with a surfactant. Chloroform-methanol extracts of kudzu leaves and stems treated with M. verrucaria spores were less cytotoxic to four cultured mammalian cell lines than the corresponding extracts from control plants. Purified macrocyclic trichothecenes (verrucarin A and T-2 toxin) were very cytotoxic to the same cell lines (< or = 2 ng/ml). These results show that neither intact macrocyclic trichothecenes nor toxic metabolites could be detected in plant tissues after treatment with M. verrucaria spores. These results argue for both safety and efficacy for the

  13. Synthesis of Cycloveratrylene Macrocycles and Benzyl Oligomers Catalysed by Bentonite under Microwave/Infrared and Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Manuel Salmón

    2013-10-01

    Full Text Available Tonsil Actisil FF, which is a commercial bentonitic clay, promotes the formation of cycloveratrylene macrocycles and benzyl oligomers from the corresponding benzyl alcohols in good yields under microwave heating and infrared irradiation in the absence of solvent in both cases. The catalytic reaction is sensitive to the type of substituent on the aromatic ring. Thus, when benzyl alcohol was substituted with a methylenedioxy, two methoxy or three methoxy groups, a cyclooligomerisation process was induced. Unsubstituted, methyl and methoxy benzyl alcohols yielded linear oligomers. In addition, computational chemistry calculations were performed to establish a validated mechanistic pathway to explain the growth of the obtained linear oligomers.

  14. [Finite element analysis of the maxillary central incisor with traditional and modified crown lengthening surgery and post-core restoration in management of crown-root fracture].

    Science.gov (United States)

    Zhen, M; Wei, Y P; Hu, W J; Rong, Q G; Zhang, H

    2016-06-01

    To construct three-dimensional finite element models with modified crown lengthening surgery and post-core restoration in management of various crown-root fracture types, to investigate the intensity and distribution of stressin models mentioned above, and to compare and analyze the indications of traditional and modified crown lengthening surgeries from the mechanic point of view. Nine three-dimensional finite element models with modified crown lengthening surgery and post-core restoration were established and analyzed by micro-CT scanning technique, dental impression scanner, Mimics 10.0, Geomagic studio 9.0 and ANSYS 14.0 software. The von Mises stress of dentin, periodontal ligament, alveolar bone, post and core, as well as the periodontal ligament area and threshold limit value were calculated and compared with the findings of traditional crown lengthening models which had been published earlierby our research group. The von Mises stress intensity of modified crown lengthening models were: dentin>post>core>alveolar bone>periodontal ligament. The maximum von Mises stress of dentin(44.37-80.58 MPa)distributed in lingual central shoulder. The periodontal ligament area of the modified crown lengthening surgery was reduced by 6% to 28%, under the same crown-root fracture conditions, the periodontal ligament area of modified crown lengthening models was larger than that of the traditional crown lengthening models. In modified crown lengthening surgery models, the von Mises stress of periodontal ligament of B3L1m, B3L2m, B3L3m models exceeded their limit values, however, the von Mises stress of periodontal ligament of the B2L2c, B2L3c, B3L1c, B3L2c, B3L3c models exceeded their limit values in traditional crown lengthening surgery models. The modified crown lengthening surgery conserves more periodontal supporting tissues, which facilitates the long-term survival of teeth. The indication of modified crown lengthening surgery is wider than traditional method. The

  15. Evaluation of the larval migration inhibition assay for detecting macrocyclic lactone resistance in Dirofilaria immitis.

    Science.gov (United States)

    Evans, Christopher C; Moorhead, Andrew R; Storey, Bobby E; Blagburn, Byron L; Wolstenholme, Adrian J; Kaplan, Ray M

    2017-11-15

    Anthelmintics of the macrocyclic lactone (ML) drug class are widely used as preventives against the canine heartworm (Dirofilaria immitis). Over the past several years, however, reports of ML lack of efficacy (LOE) have emerged, in which dogs develop mature heartworm infection despite the administration of monthly prophylactics. More recently, isolates from LOE cases have been used to infect laboratory dogs and the resistant phenotype has been confirmed by the establishment of adult worms in the face of ML treatment at normally preventive dosages. Testing for and monitoring resistance in D. immitis requires a validated biological or molecular diagnostic assay. In this study, we assessed a larval migration inhibition assay (LMIA) that we previously optimized for use with D. immitis third-stage larvae (L 3 ). We used this assay to measure the in vitro ML susceptibilities of a known-susceptible laboratory strain of D. immitis and three highly suspected ML-resistant isolates originating from three separate LOE cases; progeny from two of these isolates have been confirmed ML-resistant by treatment of an infected dog in a controlled setting. A nonlinear regression model was fit to the dose-response data, from which IC 50 values were calculated. The D. immitis LMIA yielded consistent and reproducible dose-response data; however, no statistically significant differences in drug susceptibility were observed between control and LOE parasites. Additionally, the drug concentrations needed to paralyze the L 3 were much higher than those third- and fourth-stage larvae would experience in vivo. IC 50 values ranged from 1.57 to 5.56μM (p≥0.19). These data could suggest that ML resistance in this parasite is not mediated through a reduced susceptibility of L 3 to the paralytic effects of ML drugs, and therefore motility-based assays are likely not appropriate for measuring the effects of MLs against D. immitis in this target stage. Published by Elsevier B.V.

  16. Development of an in vitro bioassay for measuring susceptibility to macrocyclic lactone anthelmintics in Dirofilaria immitis.

    Science.gov (United States)

    Evans, Christopher C; Moorhead, Andrew R; Storey, Bobby E; Wolstenholme, Adrian J; Kaplan, Ray M

    2013-12-01

    For more than 20 years, anthelmintics of the macrocyclic lactone (ML) drug class have been widely and effectively used as preventives against the canine heartworm, Dirofilaria immitis. However, in recent years an increased number of lack of efficacy (LOE) cases are being reported, in which dogs develop mature heartworm infections despite receiving monthly prophylactic doses of ML drugs. While this situation is raising concerns that heartworms may be developing resistance to MLs, compelling evidence for this is still lacking. Resolution of this dilemma requires validated biological or molecular diagnostic assays, but, unfortunately, no such tests currently exist. To address this need, we developed and optimized a larval migration inhibition assay (LMIA) for use with D. immitis third-stage larvae. The LMIA was used to measure the in vitro dose-response of two ML drugs (ivermectin and eprinomectin) on a known ML-susceptible laboratory strain of D. immitis. A nonlinear regression model was fit to the dose-response data, from which IC50 values were calculated; the mean IC50 and 95% confidence interval for IVM was 4.56 μM (1.26-16.4 μM), greater than that for EPR at 2.02 μM (1.68-2.42 μM), and this difference was significant (p = 0.0428). The R (2) value for EPR assays (0.90) was also greater than that for IVM treatment (0.71). The consistency and reproducibility of the dose-response data obtained with this assay suggests that it may be a useful technique for investigating the relative susceptibilities to ML drugs in other D. immitis populations.

  17. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand; Complejos de disprosio con el ligante macrociclico tetrafenilporfirina

    Energy Technology Data Exchange (ETDEWEB)

    Martinez M, V.; Padilla, J.; Ramirez, F.M

    1992-04-15

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H{sub 2}TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac){sub 3}. H{sub 2}0] and trihydrated [Dy(acac){sub 3} .3 H{sub 2}0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP){sub 2}] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP){sub 3}. 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP){sup 2-} (TFP) {sup 1-}] for the Dy(TFP){sub 2} as a result of the existence of the free radical (TFP' {sup 1-} and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  18. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand; Complejos de disprosio con el ligante macrociclico tetrafenilporfirina

    Energy Technology Data Exchange (ETDEWEB)

    Martinez M, V; Padilla, J; Ramirez, F M

    1992-04-15

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H{sub 2}TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac){sub 3}. H{sub 2}0] and trihydrated [Dy(acac){sub 3} .3 H{sub 2}0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP){sub 2}] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP){sub 3}. 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP){sup 2-} (TFP) {sup 1-}] for the Dy(TFP){sub 2} as a result of the existence of the free radical (TFP' {sup 1-} and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  19. Fracture toughness of zirconia ceramic crowns made by feather-edge tooth preparation design

    Directory of Open Access Journals (Sweden)

    Mirković Nemanja

    2012-01-01

    Full Text Available Background/Aim. Fracture toughness determines functional crown strenght and prevents damages on ceramics during mastication. There is a lack of relevant literature data about fracture toughness of crowns made by feather-edge preparation. Mechanical testing of ceramic samples is supposed to show if feather-edge tooth preparation is a successful method for making ceramic crowns without any risk of reduction of their mechanical properties. This research was done to establish effects of feather-edge tooth preparation on fracture toughness of single zirconia ceramic crowns. Methods. The research was performed as an experimental study. Sixty (60 ceramic crowns were made on non-carious extracted human premolars. Thirty (30 crowns were made on the basis of feather-edge preparation (experimental group I. The group II included 30 crowns made on 1 mm rounded shoulder. Crowns fabrication was executed on a copy mill production system “Zirkonzahn” (Zirkonzahn GMBH, Gais, Germany. The spherical compression test was used to determine fracture toughness, using 6 mm diameter ceramic ball. Fracture load for damaging ceramic crown was recorded on a universal testing machine - Zwick, type 1464, with the speed of 0.05 mm/min. Results. The results of this research introduced significant differences between fracture toughness of ceramic samples in every examined group. However, fracture toughness of crowns from both group was above 2 000 N, what was double beyond a recommended value. The mean value of fracture toughness in the feather-edge group was 2 090 N, and in shoulder group it was 2 214 N. Conclusion. This research showed a high fracture toughness of zirconia crowns made on feather-edge preparation. The examined crowns showed a fracture resistance at a sufficient distance in relation to the minimum values of functional loads. Further research of functional loads of these crown is necessary, as well as research of marginal adaptation of cemented crowns and

  20. Fracture rates of IPS Empress all-ceramic crowns--a systematic review.

    Science.gov (United States)

    Heintze, Siegward D; Rousson, Valentin

    2010-01-01

    The aim of this study was to evaluate the clinical fracture rate of crowns fabricated with the pressable, leucite-reinforced ceramic IPS Empress, and relate the results to the type of tooth restored. The database SCOPUS was searched for clinical studies involving full-coverage crowns made of IPS Empress. To assess the fracture rate of the crowns in relation to the type of restored tooth and study, Poisson regression analysis was used. Seven clinical studies were identified involving 1,487 adhesively luted crowns (mean observation time: 4.5+/-1.7 years) and 81 crowns cemented with zinc-phosphate cement (mean observation time: 1.6+/-0.8 years). Fifty-seven of the adhesively luted crowns fractured (3.8%). The majority of fractures (62%) occurred between the third and sixth year after placement. There was no significant influence regarding the test center on fracture rate, but the restored tooth type played a significant role. The hazard rate (per year) for crowns was estimated to be 5 in every 1,000 crowns for incisors, 7 in every 1,000 crowns for premolars, 12 in every 1,000 crowns for canines, and 16 in every 1,000 crowns for molars. One molar crown in the zinc-phosphate group fractured after 1.2 years. Adhesively luted IPS Empress crowns showed a low fracture rate for incisors and premolars and a somewhat higher rate for molars and canines. The sample size of the conventionally luted crowns was too small and the observation period too short to draw meaningful conclusions.

  1. Retention of metal-ceramic crowns with contemporary dental cements.

    Science.gov (United States)

    Johnson, Glen H; Lepe, Xavier; Zhang, Hai; Wataha, John C

    2009-09-01

    New types of crown and bridge cement are in use by practitioners, and independent studies are needed to assess their effectiveness. The authors conducted a study in three parts (study A, study B, and study C) and to determine how well these new cements retain metal-ceramic crowns. The authors prepared teeth with a 20-degree taper and a 4-millimeter length. They cast high-noble metal-ceramic copings, then fitted and cemented them with a force of 196 newtons. The types of cements they used were zinc phosphate, resin-modified glass ionomer, conventional resin and self-adhesive modified resin. They thermally cycled the cemented copings, then removed them. They recorded the removal force and calculated the stress of dislodgment by using the surface area of each preparation. They used a single-factor analysis of variance to analyze the data (alpha = .05). The mean stresses necessary to remove crowns, in megapascals, were 8.0 for RelyX Luting (3M ESPE, St. Paul, Minn.), 7.3 for RelyX Unicem (3M ESPE), 5.7 for Panavia F (Kuraray America, New York) and 4.0 for Fuji Plus (GC America, Alsip, Ill.) in study A; 8.1 for RelyX Luting, 2.6 for RelyX Luting Plus (3M ESPE) and 2.8 for Fuji CEM (GC America) in study B; and 4.9 for Maxcem (Kerr, Orange, Calif.), 4.0 for BisCem (Bisco, Schaumburg, Ill.), 3.7 for RelyX Unicem Clicker (3M ESPE), 2.9 for iCEM (Heraeus Kulzer, Armonk, N.Y.) and 2.3 for Fleck's Zinc Cement (Keystone Industries, Cherry Hill, N.J.) in study C. Powder-liquid versions of new cements were significantly more retentive than were paste-paste versions of the same cements. The mean value of crown removal stress for the new self-adhesive modified-resin cements varied appreciably among the four cements tested. All cements retained castings as well as or better than did zinc phosphate cement. Powder-liquid versions of cements, although less convenient to mix, may be a better clinical choice when crown retention is an issue. All cements tested will retain castings

  2. Descriptive statistics of tree crown condition in the Southern United States and impacts on data analysis and interpretation

    Science.gov (United States)

    KaDonna C. Randolph

    2006-01-01

    The U.S. Department of Agriculture Forest Service, Forest Inventory and Analysis Program (FIA) utilizes visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes and discusses distributions of three FIA crown condition indicators (crown density, crown dieback, and foliage transparency) for trees in the Southern...

  3. Comparative evaluation of marginal leakage of provisional crowns cemented with different temporary luting cements: In vitro study

    Directory of Open Access Journals (Sweden)

    Sheen Juneja Arora

    2016-01-01

    Conclusion: The temporary cements with eugenol showed more microleakage than those without eugenol. SC-10 crowns showed more microleakage compared to Protemp 4 crowns. SC-10 crowns cemented with Kalzinol showed maximum microleakage and Protemp 4 crowns cemented with HY bond showed least microleakage.

  4. Ceramic molar crown reproducibility by digital workflow manufacturing: An in vitro study.

    Science.gov (United States)

    Jeong, Ii-Do; Kim, Woong-Chul; Park, Jinyoung; Kim, Chong-Myeong; Kim, Ji-Hwan

    2017-08-01

    This in vitro study aimed to analyze and compare the reproducibility of zirconia and lithium disilicate crowns manufactured by digital workflow. A typodont model with a prepped upper first molar was set in a phantom head, and a digital impression was obtained with a video intraoral scanner (CEREC Omnicam; Sirona GmbH), from which a single crown was designed and manufactured with CAD/CAM into a zirconia crown and lithium disilicate crown (n=12). Reproducibility of each crown was quantitatively retrieved by superimposing the digitized data of the crown in 3D inspection software, and differences were graphically mapped in color. Areas with large differences were analyzed with digital microscopy. Mean quadratic deviations (RMS) quantitatively obtained from each ceramic group were statistically analyzed with Student's t-test (α=.05). The RMS value of lithium disilicate crown was 29.2 (4.1) µm and 17.6 (5.5) µm on the outer and inner surfaces, respectively, whereas these values were 18.6 (2.0) µm and 20.6 (5.1) µm for the zirconia crown. Reproducibility of zirconia and lithium disilicate crowns had a statistically significant difference only on the outer surface ( P <.001). The outer surface of lithium disilicate crown showed over-contouring on the buccal surface and under-contouring on the inner occlusal surface. The outer surface of zirconia crown showed both over- and under-contouring on the buccal surface, and the inner surface showed under-contouring in the marginal areas. Restoration manufacturing by digital workflow will enhance the reproducibility of zirconia single crowns more than that of lithium disilicate single crowns.

  5. Template synthesis of poly aza macrocyclic copper(II) and nickel(II) complexes: Spectral characterization and antimicrobial studies

    Energy Technology Data Exchange (ETDEWEB)

    Gurumoorthy, P.; Ravichandran, J.; Kaliur Rahiman, A. [The New College, Chennai (India); Karthikeyan, N.; Palani, P. [Univ. of Madras, Chennai (India)

    2012-07-15

    The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-amino propylamino)ethane produce the 12-membered N{sub 3}O and 17-membered N{sub 4}O macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear N{sub 3}O and N{sub 4}O copper(II) complexes show one irreversible one electron reduction wave at E{sup pc} = .1.35 and .1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at E{sup pc} = .1.25 and .1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at Epa = +0.84 and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

  6. Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

    KAUST Repository

    Pati, Debasis

    2017-02-09

    Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

  7. Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

    KAUST Repository

    Pati, Debasis; Feng, Xiaoshuang; Hadjichristidis, Nikolaos; Gnanou, Yves

    2017-01-01

    Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

  8. Macrocyclic peptide inhibitors for the protein-protein interaction of Zaire Ebola virus protein 24 and karyopherin alpha 5.

    Science.gov (United States)

    Song, Xiao; Lu, Lu-Yi; Passioura, Toby; Suga, Hiroaki

    2017-06-21

    Ebola virus infection leads to severe hemorrhagic fever in human and non-human primates with an average case fatality rate of 50%. To date, numerous potential therapies are in development, but FDA-approved drugs or vaccines are yet unavailable. Ebola viral protein 24 (VP24) is a multifunctional protein that plays critical roles in the pathogenesis of Ebola virus infection, e.g. innate immune suppression by blocking the interaction between KPNA and PY-STAT1. Here we report macrocyclic peptide inhibitors of the VP24-KPNA5 protein-protein interaction (PPI) by means of the RaPID (Random non-standard Peptides Integrated Discovery) system. These macrocyclic peptides showed remarkably high affinity to recombinant Zaire Ebola virus VP24 (eVP24), with a dissociation constant in the single digit nanomolar range, and could also successfully disrupt the eVP24-KPNA interaction. This work provides for the first time a chemical probe capable of modulating this PPI interaction and is the starting point for the development of unique anti-viral drugs against the Ebola virus.

  9. Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

    Science.gov (United States)

    Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2014-12-21

    The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

  10. Uranium (VI) complexing by macrocyclic or chelating ligands in aqueous solutions stability, formation kinetics, polarographic properties

    International Nuclear Information System (INIS)

    Brighli, M.

    1984-07-01

    Stability of chelates (with EDTA,N,N ethylenediamine diacetic acid EDDA nitrilotriacetic acid NTA and iminodiacetic acid) of UO 2 2+ and UO 4 species of uranium VI is studied in aqueous solution (NaClO 4 3M at 25 deg celcius). Structure in solution are proposed and discussed for mononuclear species. Only complexing kinetics (formation and acid hydrolysis) of UO 4 with EDDA and NTA are studied by spectrophotometry (other reactions are too fast). Besides UO 2 2+ complexes are formed with crown ethers I5C5 and I8C6 in aqueous solution (TEA ClO 4 M/10 at 25 deg celcius. Complexes are probably stabilized by solvation. Results are confirmed by voltametry and reduction mechanisms of UO 2 2+ and its complexes on mercury drop are proposed. 143 refs [fr

  11. Fabrication of reduced graphene oxide/macrocyclic cobalt complex nanocomposites as counter electrodes for Pt-free dye-sensitized solar cells

    Science.gov (United States)

    Tsai, Chih-Hung; Shih, Chun-Jyun; Wang, Wun-Shiuan; Chi, Wen-Feng; Huang, Wei-Chih; Hu, Yu-Chung; Yu, Yuan-Hsiang

    2018-03-01

    In this study, macrocyclic Co complexes were successfully grafted onto graphene oxide (GO) to produce GO/Co nanocomposites with a large surface area, high electrical conductivity, and excellent catalytic properties. The novel GO/Co nanocomposites were applied as counter electrodes for Pt-free dye-sensitized solar cells (DSSCs). Various ratios of macrocyclic Co complexes were used as the reductant to react with the GO, with which the surface functional groups of the GO were reduced and the macrocyclic ligand of the Co complexes underwent oxidative dehydrogenation, after which the conjugated macrocyclic Co systems were grafted onto the surface of the reduced GO to form GO/Co nanocomposites. The surface morphology, material structure, and composition of the GO/Co composites and their influences on the power-conversion efficiency of DSSC devices were comprehensively investigated. The results showed that the GO/Co (1:10) counter electrode (CE) exhibited an optimal power conversion efficiency of 7.48%, which was higher than that of the Pt CE. The GO/Co (1:10) CE exhibited superior electric conductivity, catalytic capacity, and redox capacity. Because GO/Co (1:10) CEs are more efficient and cheaper than Pt CEs, they could potentially be used as a replacement for Pt electrodes.

  12. Microscale Synthesis, Reactions, and (Super 1)H NMR Spectroscopic Investigations of Square Planar Macrocyclic, Tetramido-N Co(III) Complexes Relevant to Green Chemistry

    Science.gov (United States)

    Watson, Tanya T.; Uffelman, Erich S.; Lee, Daniel W., III; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen, R.

    2004-01-01

    The microscale preparation, characterization, and reactivity of a square planar Co(III) complex that has grown out of a program to introduce experiments of relevance to green chemistry into the undergraduate curriculum is presented. The given experiments illustrate the remarkable redox and aqueous acid-base stability that make the macrocycles very…

  13. Genetic profiles of ten Dirofilaria immitis isolates susceptible or resistant to macrocyclic lactone heartworm preventives

    Directory of Open Access Journals (Sweden)

    Catherine Bourguinat

    2017-11-01

    Full Text Available Abstract Background For dogs and cats, chemoprophylaxis with macrocyclic lactone (ML preventives for heartworm disease is widely used in the United States and other countries. Since 2005, cases of loss of efficacy (LOE of heartworm preventives have been reported in the U.S. More recently, ML-resistant D. immitis isolates were confirmed. Previous work identified 42 genetic markers that could predict ML response in individual samples. For field surveillance, it would be more appropriate to work on microfilarial pools from individual dogs with a smaller subset of genetic markers. Methods MiSeq technology was used to identify allele frequencies with the 42 genetic markers previously reported. Microfilaria from ten well-characterized new isolates called ZoeKY, ZoeMI, ZoeGCFL, ZoeAL, ZoeMP3, ZoeMO, ZoeAMAL, ZoeLA, ZoeJYD-34, and Metairie were extracted from fresh blood from dogs. DNA were extracted and sequenced with MiSeq technology. Allele frequencies were calculated and compared with the previously reported susceptible, LOE, and resistant D. immitis populations. Results The allele frequencies identified in the current resistant and susceptible isolates were in accordance with the allele frequencies previously reported in related phenotypes. The ZoeMO population, a subset of the ZoeJYD-34 population, showed a genetic profile that was consistent with some reversion towards susceptibility compared with the parental ZoeJYD-34 population. The Random Forest algorithm was used to create a predictive model using different SNPs. The model with a combination of three SNPs (NODE_42411_RC, NODE_21554_RC, and NODE_45689 appears to be suitable for future monitoring. Conclusions MiSeq technology provided a suitable methodology to work with the microfilarial samples. The list of SNPs that showed good predictability for ML resistance was narrowed. Additional phenotypically well characterized D. immitis isolates are required to finalize the best set of SNPs to be

  14. Cyanide Scavenging by a Cobalt Schiff-Base Macrocycle: A Cost-Effective Alternative to Corrinoids.

    Science.gov (United States)

    Lopez-Manzano, Elisenda; Cronican, Andrea A; Frawley, Kristin L; Peterson, Jim; Pearce, Linda L

    2016-06-20

    The complex of cobalt(II) with the ligand 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17)2,11,13,15-pentaene (CoN4[11.3.1]) has been shown to bind two molecules of cyanide in a cooperative fashion with an association constant of 2.7 (±0.2) × 10(5). In vivo, irrespective of whether it is initially administered as the Co(II) or Co(III) cation, EPR spectroscopic measurements on blood samples show that at physiological levels of reductant (principally ascorbate) CoN4[11.3.1] becomes quantitatively reduced to the Co(II) form. However, following addition of sodium cyanide, a dicyano Co(III) species is formed, both in blood and in buffered aqueous solution at neutral pH. In keeping with other cobalt-containing cyanide-scavenging macrocycles like cobinamide and cobalt(III) meso-tetra(4-N-methylpyridyl)porphine, we found that CoN4[11.3.1] exhibits rapid oxygen turnover in the presence of the physiological reductant ascorbate. This behavior could potentially render CoN4[11.3.1] cytotoxic and/or interfere with evaluations of the antidotal capability of the complex toward cyanide through respirometric measurements, particularly since cyanide rapidly inhibits this process, adding further complexity. A sublethal mouse model was used to assess the effectiveness of CoN4[11.3.1] as a potential cyanide antidote. The administration of CoN4[11.3.1] prophylactically to sodium cyanide-intoxicated mice resulted in the time required for the surviving animals to recover from "knockdown" (unconsciousness) being significantly decreased (3 ± 2 min) compared to that of the controls (22 ± 5 min). All observations are consistent with the demonstrated antidotal activity of CoN4[11.3.1] operating through a cyanide-scavenging mechanism, which is associated with a Co(II) → Co(III) oxidation of the cation. To test for postintoxication neuromuscular sequelae, the ability of mice to remain in position on a rotating cylinder (RotaRod test) was assessed during and after recovery

  15. Crown condition assessment at the CONECOFOR Permanent Monitoring Plots

    Directory of Open Access Journals (Sweden)

    Renzo NIBBI

    2002-09-01

    Full Text Available A detailed crown condition assessment is currently being carried out at the CONECOFOR (CONtrollo ECOsistemi FORestali, Control of Forest Ecosystems plots. The assessment began in 1996, and during the first two years (1996 and 1997 an assessment form based on previous regional experience was used; in 1998 the new official EU form was adopted. The resulting loss of comparability means that only a few indices can be used in the temporal series 1996-1999. Much effort was devoted to Quality Assurance (QA procedures. The QA program is structured as follows: (i specific field manuals have been adopted and are continuously updated; (ii a national training and intercalibration course (NT&IC is undertaken yearly before beginning the assessment campaign;( iii field checks are carried out yearly on a large number of plots. The results of the QA program have shown that for several indices the quality objectives were not reached, but the quality of the data is improving with time. To express the change in crown conditions in each area, a complex index (CCI = Crown Condition Index was adopted. This index is the result of the sum of the relativized values of all the common indices used during the four years. The following parameters were used: transparency, ramification type, leaf colour alteration extension, leaf damage extension, alteration of leaf distension extension. The range within which the CCI fluctuates was evaluated taking into account all the observations carried out at a given plot throughout the years. The number of cases over a given threshold (outliers was calculated for each year. The threshold for outliers was calculated as the median value plus 2 times the range of the interquartile value. All individual cases exceeding this value are considered outliers. The results are presented for all the areas in which the data set is complete for the four years. The yearly fluctuations are discussed and related to possible causes.

  16. RICHMOND CROWN - FOR RESTORATION OF BADLY MUTILATED POSTERIOR TEETH : A CASE REPORT

    Directory of Open Access Journals (Sweden)

    Yadav

    2015-07-01

    Full Text Available Restoration of badly broken endodontically treated teeth is a common problem in restorative dentistry. Such teeth often require additional support from the root canal by means of a post and core restoration. In cases where tooth structure is significantly lost full coverage restorations for posterior teeth are necessary to achieve proper tooth form and function. Badly broken teeth with minimal or no crown structure require added retention and support. The Richmond crown can be a good treatment alternative for restoration of such teeth. The Richmond crown was introduced in 1878 and incorporated a threaded tube in the canal with a screw retained crown. It was later modified to eliminate the threaded tube and was redesigned as a one piece dowel and crown. This case report shows restoration of badly mutilated posterior teeth with Richmond crown.

  17. Kinetically inert lanthanide complexes as reporter groups for binding of potassium by 18-crown-6

    DEFF Research Database (Denmark)

    Junker, Anne Kathrine Ravnsborg; Tropiano, Manuel; Faulkner, Stephen

    2016-01-01

    in a copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) “click” reaction with azide-functionalized crown ethers. The resulting complexes were investigated using NMR and optical methods. Titrations with potassium chloride in methanol observing the sensititzed europium- and terbium-centered emissions were......-centered emission to report on the binding of potassium in an 18-crown-6 binding pocket. The responsive systems were made by linking a crown ether to a kinetically inert lanthanide binding pocket using a molecular building block approach. Specifically, an alkyne-appended Ln.DO3A was used as a building block...... used to investigate the response of the systems. The molecular reporters based on aliphatic crown ethers were found to have strongly inhibited binding of potassium, while the benzo-18-crown-6 derived systems had essentially the same association constants as the native crown ethers. The shape...

  18. [Clinical application of IPS-empress 2 pressable all-ceramic crowns].

    Science.gov (United States)

    Wang, Ai-jun; He, Xiao-ming; Liu, Li-xia; Zhang, Chao-biao; Zhang, Min; Shen, Bei-yong

    2007-02-01

    To evaluate the clinical prosthetic effect of IPS-Empress 2 pressahie ceramic crowns. 198 teeth of 70 patients were restored with IPS-Empress 2 pressahie ceramic crowns. The patients were asked to return in one week and every half year. The clinical prosthetic effect was evaluated. Through follow-up of 3-38 months, the veneer porcelain crowns of 3 teeth were broken. 2 crowns fall off due to teeth fracture, gingivitis occurred in 2 teeth, pulpitis or periapical periodontitis occurred in 3 teeth. The shades of 3 crowns were darkening. The prosthetic effect of 185 teeth was satisfied. The rate of satisfaction was 93.4%. IPS-Empress 2 pressable all-ceramic crown has the advantages of aesthetic effect, good hiocompatihility and simple fabrication. But its strength is not enough for posterior teeth and it can not cover the deep color of non-vital teeth and metal materials.

  19. Bis(hydroxyammonium hexachloridoplatinate(IV–18-crown-6 (1/2

    Directory of Open Access Journals (Sweden)

    Evgeny Bulatov

    2014-01-01

    Full Text Available In the title complex, (NH3OH2[PtCl6]·2C12H24O6, the PtIV atom is coordinated by six chloride anions in a slightly distorted octahedral geometry. The Pt—Cl bond lengths are comparable to those reported for other hexachloridoplatinate(IV species. The hydroxyammonium groups act as linkers between the [PtCl6]2− anion and the crown ether molecules. The anion is linked to two hydroxyammonium cations via O—H...Cl hydrogen bonds and each hydroxyammonium moiety is linked to a crown ether molecule by hydrogen bonds between ammonium H atoms and 18-crown-6 O atoms. The crown ether molecules have the classic crown shape in which all O atoms are located in the inner part of the crown ether ring and all –CH2– groups are turned to the outside.

  20. Suppressing Nonradiative Recombination in Crown-Shaped Quantum Wells

    Energy Technology Data Exchange (ETDEWEB)

    Park, Kwangwook [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ju, Gunwu [Gwangju Institute of Science and Technology; Korea Institute of Science and Technology; Na, Byung Hoon [Samsung Advanced Institute of Technology; Hwang, Hyeong-Yong [Gwangju Institute of Science and Technology; Jho, Young-Dahl [Gwangju Institute of Science and Technology; Myoung, NoSoung [Gwangju Institute of Science and Technology; Yim, Sang-Youp [Gwangju Institute of Science and Technology; Kim, Hyung-jun [Korea Institute of Science and Technology; Lee, Yong Tak [Gwangju Institute of Science and Technology

    2018-02-06

    We examined the structural and optical properties of a crown-shaped quantum well (CSQW) to suppress nonradiative recombination. To reduce carrier loss in defect traps at the well/barrier interface, the CSQW was designed to concentrate carriers in the central region by tailoring the bandgap energy. Temperature-dependent photoluminescence measurements showed that the CSQW had a high activation energy and low potential fluctuation. In addition, the long carrier lifetime of the CSQW at high temperatures can be interpreted as indicating a decrease in carrier loss at defect traps.

  1. Radiochemical determination of 210Pb using crown ether

    International Nuclear Information System (INIS)

    Vajda, N.; Bodizs, D.; Vodicska, M.

    1994-01-01

    Gamma spectrometric determination of 210 Pb following chemical separation has been performed very precisely and with high sensitivity, due to the low and constant self-absorption of the chemically pure sample. A simple and quick method for the chemical separation of lead using crown ether has been developed. Its four steps are described in detail. The new method was verified using phosphate ore and gypsum samples that were measured in an interlaboratory comparison and with a standard reference material. This method can also be used for self-absorption correction in direct gamma spectrometry of 210 Pb. (N.T.) 4 refs.; 2 figs.; 2 tabs

  2. Short Note: New breeding locality for Crowned Cormorant

    Directory of Open Access Journals (Sweden)

    P.A. Whittington

    2004-12-01

    Full Text Available The Crowned Cormorant Phalacrocorax coronatus is endemic to the southern African subregion with an estimated population of about 2700 pairs, breeding at 48 localities between Walvis Bay, Namibia and Cape Agulhas, South Africa (Crawford et al. 1994, Crawford 1997. The easternmost point at which breeding has previously been recorded is 2 km west of Aasfontein (34°46'S, 19°50'E, where 35 nests were recorded in January 1981 (Crawford et al. 1982. Non-breeding birds have been seen further to the east as far as Holkom Meester se Baai (34°23'S, 21°49'E (Crawford et al. 1982.

  3. Use of crown compounds and cryptands in analytical chemistry

    International Nuclear Information System (INIS)

    Blazius, Eh.; Yansen, K.P.

    1988-01-01

    Possibilities of crown compound and crypton application in amalytical chemistry for separation (extraction, chromatography) and determination of different cations and anions are considered. It is marked that monomeric cyclic polyethers are mainly used for separation and determination of alkali and alkaline earth metals. Linear polymers of cyclic polyethers are exclusively used for extraction of their salts. Cross-linked polymeric cyclic polyethers permit to carry out the separation and determination of most of cations (including transition, rare earth elements, actinides), anions and organic compounds. 99 refs.; 10 figs.; 8 tabs

  4. Fracture Strength of Aged Monolithic and Bilayer Zirconia-Based Crowns

    Directory of Open Access Journals (Sweden)

    Deborah Pacheco Lameira

    2015-01-01

    Full Text Available The purpose of this study was to evaluate the effect of design and surface finishing on fracture strength of yttria-tetragonal zirconia polycrystal (Y-TZP crowns in monolithic (1.5 mm thickness and bilayer (0.8 mm zirconia coping and 0.7 mm porcelain veneer configuration after artificial aging. Bovine incisors received crown preparation and Y-TZP crowns were manufactured using CAD/CAM technique, according to the following groups (n=10: Polished monolithic zirconia crowns (PM; Glazed monolithic zirconia crowns (GM; Bi-layer crowns (BL. Crowns were cemented with resin cement, submitted to artificial aging in a chewing simulator (2.5 million cycles/80 N/artificial saliva/37°C, and tested for fracture strength. Two remaining crowns referring to PM and GM groups were submitted to a chemical composition analysis to measure the level of yttrium after aging. One-way ANOVA and Tukey’s test (P=.05 indicated that monolithic zirconia crowns presented similar fracture strength (PM=3476.2 N ± 791.7; GM=3561.5 N ± 991.6, which was higher than bilayer crowns (2060.4 N ± 810.6. There was no difference in the yttrium content among the three surfaces evaluated in the monolithic crowns. Thus, monolithic zirconia crowns present higher fracture strength than bilayer veneered zirconia after artificial aging and surface finishing does not affect their fracture strength.

  5. Composite Bonding to Stainless Steel Crowns Using a New Universal Bonding and Single-Bottle Systems

    OpenAIRE

    Mohammad Ali Hattan; Sharat Chandra Pani; Mohammad AlOmari

    2013-01-01

    Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80) stainless steel crowns (SSCs) were divided into four groups (20 each). Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group), Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany), ...

  6. DNA methylation mediated control of gene expression is critical for development of crown gall tumors.

    Directory of Open Access Journals (Sweden)

    Jochen Gohlke

    Full Text Available Crown gall tumors develop after integration of the T-DNA of virulent Agrobacterium tumefaciens strains into the plant genome. Expression of the T-DNA-encoded oncogenes triggers proliferation and differentiation of transformed plant cells. Crown gall development is known to be accompanied by global changes in transcription, metabolite levels, and physiological processes. High levels of abscisic acid (ABA in crown galls regulate expression of drought stress responsive genes and mediate drought stress acclimation, which is essential for wild-type-like tumor growth. An impact of epigenetic processes such as DNA methylation on crown gall development has been suggested; however, it has not yet been investigated comprehensively. In this study, the methylation pattern of Arabidopsis thaliana crown galls was analyzed on a genome-wide scale as well as at the single gene level. Bisulfite sequencing analysis revealed that the oncogenes Ipt, IaaH, and IaaM were unmethylated in crown galls. Nevertheless, the oncogenes were susceptible to siRNA-mediated methylation, which inhibited their expression and subsequently crown gall growth. Genome arrays, hybridized with methylated DNA obtained by immunoprecipitation, revealed a globally hypermethylated crown gall genome, while promoters were rather hypomethylated. Mutants with reduced non-CG methylation developed larger tumors than the wild-type controls, indicating that hypermethylation inhibits plant tumor growth. The differential methylation pattern of crown galls and the stem tissue from which they originate correlated with transcriptional changes. Genes known to be transcriptionally inhibited by ABA and methylated in crown galls became promoter methylated upon treatment of A. thaliana with ABA. This suggests that the high ABA levels in crown galls may mediate DNA methylation and regulate expression of genes involved in drought stress protection. In summary, our studies provide evidence that epigenetic processes

  7. Fatigue resistance and microleakage of CAD/CAM ceramic and composite molar crowns.

    Science.gov (United States)

    Kassem, Amr S; Atta, Osama; El-Mowafy, Omar

    2012-01-01

    The aim of this study was to determine effect of compressive cyclic loading on fatigue resistance and microleakage of monolithic CAD/CAM molar ceramic and composite crowns. Thirty-two extracted molars were prepared to receive CEREC crowns according to manufacturer's guidelines using a special paralleling device (Parallel-A-Prep). Sixteen feldspathic ceramic crowns (VITABLOCS Mark II) (VMII) and 16 resin-composite crowns (Paradigm-MZ100 blocks) (PMZ) were milled using a CEREC-3D machine. Eight crowns of each group were cemented to their respective teeth using self-etching resin cement (Panavia-F-2.0) (PAN), and eight were cemented using self-adhesive resin cement (RelyX-Unicem-Clicker) (RXU). Following storage for 1 week in water, specimens were subjected to uniaxial compressive cyclic loading in an Instron testing machine at 12 Hz for 1,000,000 cycles. Load was applied at the central fossa, and the cycle range was 60-600 N. Specimens were then subjected to microleakage testing. Data were statistically analyzed using factorial ANOVA and Post Hoc (Tukey HSD) tests. All composite crowns survived compressive cyclic loading without fracture, while three ceramic crowns from the subgroup cemented with RXU developed surface cracks at the center of occlusal surfaces, extending laterally. Microleakage scores of ceramic crowns cemented with PAN were significantly lower than those of the other three subgroups (p < 0.05). After 1,000,000 cycles of compressive cyclic loading, PMZ composite molar crowns were more fatigue-resistant than VMII ceramic crowns. Cement type had a significant effect on fatigue resistance of the ceramic crowns but not the composite ones. Microleakage scores of ceramic crowns cemented with PAN were significantly lower than those of the other subgroups (p < 0.05). © 2011 by The American College of Prosthodontists.

  8. Influence of ionizing radiation and 12-crown-4 on coagulation system components of rat blood

    International Nuclear Information System (INIS)

    Kratenko, R.Yi.

    2006-01-01

    The influence of 12-crown-4 and ionizing radiation on some components of blood coagulation system: Ca 2+ contents and prostaglandin concentrations in the blood serum, and erythrocyte contents in the blood plasma are studied. The influence of 12-crown-4 and ionizing radiation increases the coagulational properties of erythrocytes. The synergism of ionizing irradiation and 12-crown-4 influence blood coagulation process points out at the occurrence of radiomimetic properties of the latter

  9. Stress distribution difference between Lava Ultimate full crowns and IPS e.max CAD full crowns on a natural tooth and on tooth-shaped implant abutments.

    Science.gov (United States)

    Krejci, Ivo; Daher, René

    2017-04-01

    The goal of this short communication is to present finite element analysis comparison of the stress distribution between CAD/CAM full crowns made of Lava Ultimate and of IPS e.max CAD, adhesively luted to natural teeth and to implant abutments with the shape of natural teeth. Six 3D models were prepared using a 3D content-creating software, based on a micro-CT scan of a human mandibular molar. The geometry of the full crown and of the abutment was the same for all models representing Lava Ultimate full crowns (L) and IPS e.max CAD full crowns (E) on three different abutments: prepared natural tooth (n), titanium abutment (t) and zirconia abutment (z). A static load of 400 N was applied on the vestibular and lingual cusps, and fixtures were applied to the base of the models. After running the static linear analysis, the post-processing data we analyzed. The stress values at the interface between the crown and the abutment of the Lt and Lz groups were significantly higher than the stress values at the same interface of all the other models. The high stress concentration in the adhesive at the interface between the crown and the abutment of the Lava Ultimate group on implants might be one of the factors contributing to the reported debondings of crowns.

  10. Crown condition dynamics of oak in southern Sweden 1988-1999.

    Science.gov (United States)

    Drobyshev, Igor; Anderson, Stefan; Sonesson, Kerstin

    2007-11-01

    Crown defoliation of oak (Quercus robur and Q. petraea) was analysed in 808 trees during three forest condition surveys (1988, 1993, and 1999) in the southern Sweden. From 1988 to 1999 crown defoliation increased by more than 20%. Changes in crown defoliation were related to the pH in the upper 20-30 cm of the mineral soils, which was closely connected to other measures of soil fertility (cation exchange capacity, CEC and C/N ratio). Trees growing on soils with a high pH (> or =4.00, in BaCl2 filtrate), high CEC and low C/N ratio had significantly lower crown defoliation than trees growing on more acid soils (pH trees with respect to crown defoliation, indicating that decline in crown condition was not due to an age-related increase in crown transparency. Considering only trees younger than 100 years, a significant interaction was observed between changes in crown defoliation and soil pH. Trees younger than 100 years old growing on more acidic soils had a greater increase in crown transparency than trees on more basic soils between 1988 and 1999. Trees > or =100 years old had significantly higher defoliation on more acidic than on more basic soils, however defoliation dynamics of these trees over 1988-99 was not related to soil acidity. Two biotic agents (insect and fungal leaf infections) evaluated in this study did not prove to be important drivers of defoliation dynamics.

  11. CAD/CAM glass ceramics for single-tooth implant crowns: a finite element analysis.

    Science.gov (United States)

    Akça, Kvanç; Cavusoglu, Yeliz; Sagirkaya, Elcin; Aybar, Buket; Cehreli, Murat Cavit

    2013-12-01

    To evaluate the load distribution of CAD/CAM mono-ceramic crowns supported with single-tooth implants in functional area. A 3-dimensional numerical model of a soft tissue-level implant was constructed with cement-retained abutment to support glass ceramic machinable crown. Implant-abutment complex and the retained crown were embedded in a Ø 1.5 × 1.5 cm geometric matrix for evaluation of mechanical behavior of mono-ceramic CAD/CAM aluminosilicate and leucite glass crown materials. Laterally positioned axial load of 300 N was applied on the crowns. Resulting principal stresses in the mono-ceramic crowns were evaluated in relation to different glass ceramic materials. The highest compressive stresses were observed at the cervical region of the buccal aspect of the crowns and were 89.98 and 89.99 MPa, for aluminosilicate and leucite glass ceramics, respectively. The highest tensile stresses were observed at the collar of the lingual part of the crowns and were 24.54 and 25.39 MPa, respectively. Stresses induced upon 300 N static loading of CAD/CAM aluminosalicate and leucite glass ceramics are below the compressive strength of the materials. Impact loads may actuate the progress to end failure of mono-ceramic crowns supported by metallic implant abutments.

  12. Radium separation through complexation by aqueous crown ethers and ion exchange or solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Chiarizia, R.; Dietz, M.L.; Horwitz, E.P. [Argonne National Lab., IL (United States). Chemistry Div.; Burnett, W.C. [Florida State Univ., Tallahassee, FL (United States). Dept. of Oceanography

    1997-11-01

    The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-crown-7 (21C7)) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium-calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes is discussed and a possible flowchart for the determination of {sup 226}Ra/{sup 228}Ra in natural waters is presented.

  13. Extracting oil palm crown from WorldView-2 satellite image

    Science.gov (United States)

    Korom, A.; Phua, M.-H.; Hirata, Y.; Matsuura, T.

    2014-02-01

    Oil palm (OP) is the most commercial crop in Malaysia. Estimating the crowns is important for biomass estimation from high resolution satellite (HRS) image. This study examined extraction of individual OP crown from a WorldView-2 image using twofold algorithms, i.e., masking of Non-OP pixels and detection of individual OP crown based on the watershed segmentation of greyscale images. The study site was located in Beluran district, central Sabah, where matured OPs with the age ranging from 15 to 25 years old have been planted. We examined two compound vegetation indices of (NDVI+1)*DVI and NDII for masking non-OP crown areas. Using kappa statistics, an optimal threshold value was set with the highest accuracy at 90.6% for differentiating OP crown areas from Non-OP areas. After the watershed segmentation of OP crown areas with additional post-procedures, about 77% of individual OP crowns were successfully detected in comparison to the manual based delineation. Shape and location of each crown segment was then assessed based on a modified version of the goodness measures of Möller et al which was 0.3, indicating an acceptable CSGM (combined segmentation goodness measures) agreements between the automated and manually delineated crowns (perfect case is '1').

  14. Extracting oil palm crown from WorldView-2 satellite image

    International Nuclear Information System (INIS)

    Korom, A; Phua, M-H; Hirata, Y; Matsuura, T

    2014-01-01

    Oil palm (OP) is the most commercial crop in Malaysia. Estimating the crowns is important for biomass estimation from high resolution satellite (HRS) image. This study examined extraction of individual OP crown from a WorldView-2 image using twofold algorithms, i.e., masking of Non-OP pixels and detection of individual OP crown based on the watershed segmentation of greyscale images. The study site was located in Beluran district, central Sabah, where matured OPs with the age ranging from 15 to 25 years old have been planted. We examined two compound vegetation indices of (NDVI+1)*DVI and NDII for masking non-OP crown areas. Using kappa statistics, an optimal threshold value was set with the highest accuracy at 90.6% for differentiating OP crown areas from Non-OP areas. After the watershed segmentation of OP crown areas with additional post-procedures, about 77% of individual OP crowns were successfully detected in comparison to the manual based delineation. Shape and location of each crown segment was then assessed based on a modified version of the goodness measures of Möller et al which was 0.3, indicating an acceptable CSGM (combined segmentation goodness measures) agreements between the automated and manually delineated crowns (perfect case is '1')

  15. Twenty-nine-month follow-up of a paediatric zirconia dental crown.

    Science.gov (United States)

    Lopez Cazaux, Serena; Hyon, Isabelle; Prud'homme, Tony; Dajean Trutaud, Sylvie

    2017-06-14

    The aim of this paper is to present the long-term follow-up of one paediatric zirconia crown on a deciduous molar. Preformed crowns are part of the armamentarium in paediatric dentistry. In recent years, aesthetic alternatives to preformed metal crowns have been developed, first preveneered crowns and then zirconia crowns. This paper describes the restoration of a primary molar with a zirconia crown (EZ-Pedo, Loomis, California, USA) in an 8-year-old boy. In this clinical case, the protocol for the implementation and maintenance of zirconia crowns is detailed. The patient was followed up for 29 months until the natural exfoliation of his primary molar. The adaptation of the zirconia crown, the gingival health and the wear on the opposing tooth were considered. In this case, the paediatric zirconia crown allowed sustainable functional restoration while restoring a natural appearance of the tooth. © BMJ Publishing Group Ltd (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  16. Conductometric study of reaction kinetics between potassium superoxide and 18-crown-6 in dimethylsulfoxide

    International Nuclear Information System (INIS)

    Efimova, I.V.; Opejda, I.A.

    2000-01-01

    Complexing within KO 2 -18-crown-6-solvent, KOH-18-crown-6-solvent and KI-KO 2 -18-crown-6-solvent systems in dimethylsulfoxide was studied by measurement of electrical conductivity. It was shown that time variation of electrical conductivity under the given conditions was described by the Erofeev-Auramy equation, the coefficients of that equation for various systems were determined, time to reach equilibrium state was estimated. Linear dependences of electrical conductivity of KI-KO 2 salt solutions at presence of 18-crown-6 at the state of equilibrium in contrast to the component concentrations were determined [ru

  17. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    International Nuclear Information System (INIS)

    Myasoedova, T.G.; Ponomareva, A.V.; Zagorets, P.A.; Filippov, E.A.

    1984-01-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lgβ depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6

  18. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Myasoedova, T G; Ponomareva, A V; Zagorets, P A; Filippov, E A [Moskovskij Khimiko-Tekhnologicheskij Inst. (USSR)

    1984-08-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lg..beta.. depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6.

  19. SYNTHESIS OF 4’-ALLYLBENZO-3N-CROWN-N ETHERS AND THEIR MASS SPECTRA COMPARED WITH BENZO-3N-CROWN-N ETHERS

    OpenAIRE

    Anwar, Chairil

    2008-01-01

    Synthesis of 4’allylbenzo-3n-crown-n ethers was carried out by reacting demethylated eugenol with α,ω-dichloro-oligoethylene glycols in 1-butanol under basic condition. The mass spectra of 4’allylbenzo-3n-crown-n and benzo-3n-crown-n were investigated by mass spectrometry using electron impact under 70 eV of electron bombardment as ionisation method. The difference between the group of compounds is only the present of allyl moiety as a side chain at the other side of benzene ring. The first g...

  20. Influence of implant position on clinical crown length and peri-implant soft tissue dimensions at implant-supported single crowns replacing maxillary central incisors

    DEFF Research Database (Denmark)

    Peng, Min; Fei, Wei; Hosseini, Mandana

    2013-01-01

    The aims of the present study were to evaluate the influence of implant position on clinical crown length and marginal soft tissue dimensions at implant-supported single crowns of maxillary central incisors, and to validate the papilla index score (PIS). Twenty-five patients, who had lost one of ...... abutments and did not necessarily result in an increased crown length. The distal implant papilla heightwas obviously shorter, althoughthe mesial papilla height was similar to thatof the healthy dentition.The papilla index score was tested to be a valid index for papilla fill....

  1. The confusing array of tooth-colored crowns.

    Science.gov (United States)

    Christensen, Gordon J

    2003-09-01

    The venerable PFM crown or fixed prosthesis still dominates the tooth-colored restoration market. However, use of PFMs is declining slightly, as the many new all-ceramic and resin-based composite crowns and fixed-prosthesis products flood the market. Several situations may indicate the use of materials other than PFM. They include patients requiring a high level of esthetic acceptability, patients with proven or perceived allergies to the metals used in dentistry and bruxing or clenching patients with metal allergies or desire to eliminate metal from their mouths. PFM restorations have been proven during 40 years of successful use. They provide acceptable esthetics for most situations, minimal fracture during service, proven ability to serve in multiple-unit situations and excellent fit, and the profession has detailed knowledge of these restorations' advantages, disadvantages and physical characteristics. PFM restorations have only a few well-known negative characteristics. Be cautious as you elect to move from the reliability and positive history of PFM to relatively unknown types of restorations.

  2. Induced mutations for tolerance of oats to crown rust

    International Nuclear Information System (INIS)

    Simons, M.D.; Frey, K.J.

    1977-01-01

    Seeds of three oat (Avena sativa and A. abyssinica) strains were treated with ethyl methanesulphonate (EMS), and crown rust (caused by Puccinia coronata var. avenae) tolerance ratios of M 5 -derived lines were compared with untreated checks. Tolerance ratios of mutant lines tended to be distributed in both plus and minus directions. No mutant oat line had a significant increase in grain yield, but many showed significantly depressed yields. With C.I. 6665, only five of 130 mutagen-derived lines were not significantly below the check for grain yield; one of these had significantly improved tolerance. Re-treatment of selected strains from a previous EMS treatment (original cultivar was Clintland-60) gave one M 5 -derived oat line (of 100 tested) that was equal to Clintland-60 in grain yield and sustained no damage from crown rust (i.e. it had a tolerance ratio of 100). EMS treatment of the highly susceptible tetraploid C.I. 2110 resulted in both significantly increased and reduced tolerance. (author)

  3. Metabolic changes in Avena sativa crowns recovering from freezing.

    Directory of Open Access Journals (Sweden)

    Cynthia A Henson

    Full Text Available Extensive research has been conducted on cold acclimation and freezing tolerance of fall-sown cereal plants due to their economic importance; however, little has been reported on the biochemical changes occurring over time after the freezing conditions are replaced by conditions favorable for recovery and growth such as would occur during spring. In this study, GC-MS was used to detect metabolic changes in the overwintering crown tissue of oat (Avena sativa L. during a fourteen day time-course after freezing. Metabolomic analysis revealed increases in most amino acids, particularly proline, 5-oxoproline and arginine, which increased greatly in crowns that were frozen compared to controls and correlated very significantly with days after freezing. In contrast, sugar and sugar related metabolites were little changed by freezing, except sucrose and fructose which decreased dramatically. In frozen tissue all TCA cycle metabolites, especially citrate and malate, decreased in relation to unfrozen tissue. Alterations in some amino acid pools after freezing were similar to those observed in cold acclimation whereas most changes in sugar pools after freezing were not. These similarities and differences suggest that there are common as well as unique genetic mechanisms between these two environmental conditions that are crucial to the winter survival of plants.

  4. Alkali-crown ether complexes at metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

    2010-07-01

    Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

  5. Displacement of screw-retained single crowns into implants with conical internal connections.

    Science.gov (United States)

    Yilmaz, Burak; Seidt, Jeremy D; McGlumphy, Edwin A; Clelland, Nancy L

    2013-01-01

    Internal conical implant-abutment connections without platforms may lead to axial displacement of crowns during screw tightening. This displacement may affect proximal contacts, incisal edge position, or occlusion. This study aimed to measure the displacement of screw-retained single crowns into an implant in three dimensions during screw tightening by hand or via torque driver. A stereolithic acrylic resin cast was created using computed tomography data from a patient missing the maxillary right central incisor. A 4.0- × 11-mm implant was placed in the edentulous site. Five porcelain-fused-to-metal single crowns were made using "cast-to" abutments. Crowns were tried on the stereolithic model, representing the patient, and hand tightened. The spatial relationship of crowns to the model after hand tightening was determined using three-dimensional digital image correlation (3D DIC), an optical measurement technique. The crowns were then tightened using a torque driver to 20 Ncm and the relative crown positions were again recorded. Testing was repeated three times for each crown, and displacement of the crowns was compared between the hand-tightened and torqued states. Commercial image correlation software was used to analyze the data. Mean vertical and horizontal crown displacement values were calculated after torqueing. The interproximal contacts were evaluated before and after torquing using an 8-μm aluminum foil shim. There were vertical and horizontal differences in crown positions between hand tightening and torqueing. Although these were small in magnitude, detectable displacements occurred in both apical and facial directions. After hand tightening, the 8-μm shim could be dragged without tearing. However, after torque tightening, the interproximal contacts were too tight and the 8-μm shim could not be dragged without tearing. Differences between hand tightening and torque tightening should be taken into consideration during laboratory and clinical

  6. Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

    Science.gov (United States)

    Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

    2017-07-18

    The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Repurposing a Library of Human Cathepsin L Ligands: Identification of Macrocyclic Lactams as Potent Rhodesain and Trypanosoma brucei Inhibitors.

    Science.gov (United States)

    Giroud, Maude; Dietzel, Uwe; Anselm, Lilli; Banner, David; Kuglstatter, Andreas; Benz, Jörg; Blanc, Jean-Baptiste; Gaufreteau, Delphine; Liu, Haixia; Lin, Xianfeng; Stich, August; Kuhn, Bernd; Schuler, Franz; Kaiser, Marcel; Brun, Reto; Schirmeister, Tanja; Kisker, Caroline; Diederich, François; Haap, Wolfgang

    2018-04-26

    Rhodesain (RD) is a parasitic, human cathepsin L (hCatL) like cysteine protease produced by Trypanosoma brucei ( T. b.) species and a potential drug target for the treatment of human African trypanosomiasis (HAT). A library of hCatL inhibitors was screened, and macrocyclic lactams were identified as potent RD inhibitors ( K i < 10 nM), preventing the cell-growth of Trypanosoma brucei rhodesiense (IC 50 < 400 nM). SARs addressing the S2 and S3 pockets of RD were established. Three cocrystal structures with RD revealed a noncovalent binding mode of this ligand class due to oxidation of the catalytic Cys25 to a sulfenic acid (Cys-SOH) during crystallization. The P-glycoprotein efflux ratio was measured and the in vivo brain penetration in rats determined. When tested in vivo in acute HAT model, the compounds permitted up to 16.25 (vs 13.0 for untreated controls) mean days of survival.

  8. High-performance liquid chromatographic enantioseparation of monoterpene-based 2-amino carboxylic acids on macrocyclic glycopeptide-based phases.

    Science.gov (United States)

    Sipos, László; Ilisz, István; Pataj, Zoltán; Szakonyi, Zsolt; Fülöp, Ferenc; Armstrong, Daniel W; Péter, Antal

    2010-10-29

    The enantiomers of five monoterpene-based 2-amino carboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics such as teicoplanin (Astec Chirobiotic T and T2) and teicoplanin aglycone (Chirobiotic TAG) as chiral selectors. The effects of pH, the mobile phase composition, the structure of the analyte and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 10-40°C to study the effects of temperature and thermodynamic parameters on separations. Apparent thermodynamic parameters and T(iso) values were calculated from plots of ln k or ln α versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantioseparations were in most cases enthalpy driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2010 Elsevier B.V. All rights reserved.

  9. Preparations and crystal structures of 8 coordinate uranyl(VI) complexes having macrocyclic ligands derived from pyrroledicarboxialdehydes and diamines

    International Nuclear Information System (INIS)

    Komagine, J.; Takeda, M.; Takahashi, M.

    2006-01-01

    Six 8-coordinate uranyl(VI) complexes with macrocyclic Schiff base ligands derived from 2,6-pyrroledicarboxialdehyde and diamines are prepared and the crystal structures for two of them are determined focusing on the relation between the size of the ligands and U-N bond distances. No difference in average uranyl bond distances and bond angles are observed between [UO 2 (bipytn)](a) and [UO 2 (bipydmtn)](b). U-N bonds of these complexes are, however, not equal; the U-N(pyrrole) bonds [2.45(a), 2.44(b) A] are much shorter than the U-N(imine) bonds [2.67(a), 2.67(b) A]. (author)

  10. Magneto-electroluminescence effects in the single-layer organic light-emitting devices with macrocyclic aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    S.-T. Pham

    2018-02-01

    Full Text Available Magneto-electroluminescence (MEL effects are observed in single-layer organic light-emitting devices (OLEDs comprising only macrocyclic aromatic hydrocarbons (MAHs. The fluorescence devices were prepared using synthesized MAHs, namely, [n]cyclo-meta-phenylene ([n]CMP, n = 5, 6. The MEL ratio of the resulting OLED is 1%–2% in the spectral wavelength range of 400-500 nm, whereas it becomes negative (−1.5% to −2% in the range from 650 to 700 nm. The possible physical origins of the sign change in the MEL are discussed. This wavelength-dependent sign change in the MEL ratio could be a unique function for future single-layer OLEDs capable of magnetic-field-induced color changes.

  11. Magneto-electroluminescence effects in the single-layer organic light-emitting devices with macrocyclic aromatic hydrocarbons

    Science.gov (United States)

    Pham, S.-T.; Ikemoto, K.; Suzuki, K. Z.; Izumi, T.; Taka, H.; Kita, H.; Sato, S.; Isobe, H.; Mizukami, S.

    2018-02-01

    Magneto-electroluminescence (MEL) effects are observed in single-layer organic light-emitting devices (OLEDs) comprising only macrocyclic aromatic hydrocarbons (MAHs). The fluorescence devices were prepared using synthesized MAHs, namely, [n]cyclo-meta-phenylene ([n]CMP, n = 5, 6). The MEL ratio of the resulting OLED is 1%-2% in the spectral wavelength range of 400-500 nm, whereas it becomes negative (-1.5% to -2%) in the range from 650 to 700 nm. The possible physical origins of the sign change in the MEL are discussed. This wavelength-dependent sign change in the MEL ratio could be a unique function for future single-layer OLEDs capable of magnetic-field-induced color changes.

  12. Fracture Strength and Failure Mode of Maxillary Implant-Supported Provisional Single Crowns : A Comparison of Composite Resin Crowns Fabricated Directly Over PEEK Abutments and Solid Titanium Abutments

    NARCIS (Netherlands)

    Santing, H.J.; Meijer, Henny J.A.; Raghoebar, G.M.; Ozcan, M.

    2012-01-01

    Background: Polyetheretherketone (PEEK) temporary abutments have been recently introduced for making implant-supported provisional single crowns. Little information is available in the dental literature on the durability of provisional implant-supported restorations. Purpose: The objectives of this

  13. Retention Load Values of Telescopic Crowns Made of Y-TZP and CoCr with Y-TZP Secondary Crowns: Impact of Different Taper Angles

    Directory of Open Access Journals (Sweden)

    Susanne Merk

    2016-05-01

    Full Text Available This study aimed to examine and compare the retention load values (RL of different telescopic crown assemblies (Y-TZP and CoCr primary crowns with electroformed and Y-TZP secondary crowns each with three different taper angles (0°, 1° and 2°. Thirty Y-TZP primary crowns with electroformed gold copings (Z/G group and Y-TZP secondary crowns (Z/Z group and 30 CoCr primary crowns with electroformed gold copings (C/G group and Y-TZP secondary crowns (C/Z group, each with taper angles of 0°, 1° and 2°, were fabricated, respectively. With the exception of the electroformed gold copings, all specimens were Computer-Aided-Design/Computer-Aided-Manufacturing (CAD/CAM-milled, then sintered and afterwards manually adapted. In order to stabilize the gold copings, they were fixed in a tertiary structure. The secondary crowns were constructed with a hook, which ensured self-alignment with an upper chain. Afterwards, 20 pull-off test cycles were performed in a universal testing machine under artificial saliva and after weighing the secondary crowns with a 5 kg object for 20 s. Data were analyzed by one-way and two-way Analysis of Variance (ANOVA. C/Z with 1° showed higher (p = 0.009 RL than 0° and 2° tapers. C/G at 1° also showed higher (p = 0.001 RL than at tapers of 0° and 2°. Z/G and C/G at 0° showed lower RL than Z/Z and C/Z (p < 0.001. Primary crowns had no impact on the 0° group. Z/G showed lower RL as compared to C/Z within the 1° group (p = 0.007 and Z/Z in the 2° group (p = 0.006. The primary crown material had no influence on RL. Electroformed copings showed lower RL. Further investigations for 1° as well as for the long-term performance after thermomechanical aging are necessary.

  14. Turn on macrocyclic chemosensor for Al3+ ion with facile synthesis and application in live cell imaging

    Science.gov (United States)

    Ezhumalai, Dhineshkumar; Mathivanan, Iyappan; Chinnadurai, Anbuselvan

    2018-06-01

    An effort of a new Schiff base macrocyclic chemosensor, 14‑methyl‑2,6,8,12,14,18‑hexaaza‑1,7,13(1,2),4,10,16(1,4)‑hexabenzenacyclooctadecaphane‑2,5,8,11,14,17‑hexaene (me1) and 14,74‑dimethyl‑2,6,8,12,14,18‑hexaaza‑1,7,13(1,2),4,10,16(1,4)‑hexabenzenacyclooctadecadecaphane‑2,5,8,11,14,17‑hexaene (dm2), which enables selective sensing of Al3+ in aqueous DMF were synthesized by a simplistic one-step condensation reaction of macrocyclic compounds. The probe me1 and dm2 characterized by elemental analysis, FT-IR, 1H and 13C NMR, LC-MS spectral techniques. The compounds as mentioned above subjected to FE-SEM with EDS and elemental color mapping. On addition of Al3+, the fluorescent probe me1 and dm2 induces turn-on responses in both absorption and sensing spectra by a PET mechanism. The receptor me1 and dm2 serve highly selective, sensitive and turn-on detection of Al3+. Further, they did not interfere with other cations present in biological or environmental samples. The detection limit is found to be 3 μM and 5 μM. From the view of cytotoxic activity, the ability of these compounds me1 and dm2 to inhibit the growth of KB cell lines examined. The chelating functionality of compounds me1 and dm2 examined for their inhibitory properties of KB cell, live cell images. The compounds me1 and dm2 subjected to theoretical studies by DFT-B3LYP invoking the 6-31G level of theory. The energy of the HOMO and LUMO has been established.

  15. A Review on the Toxicity and Non-Target Effects of Macrocyclic Lactones in Terrestrial and Aquatic Environments

    Science.gov (United States)

    Lumaret, Jean-Pierre; Errouissi, Faiek; Floate, Kevin; Römbke, Jörg; Wardhaugh, Keith

    2012-01-01

    The avermectins, milbemycins and spinosyns are collectively referred to as macrocyclic lactones (MLs) which comprise several classes of chemicals derived from cultures of soil micro-organisms. These compounds are extensively and increasingly used in veterinary medicine and agriculture. Due to their potential effects on non-target organisms, large amounts of information on their impact in the environment has been compiled in recent years, mainly caused by legal requirements related to their marketing authorization or registration. The main objective of this paper is to critically review the present knowledge about the acute and chronic ecotoxicological effects of MLs on organisms, mainly invertebrates, in the terrestrial and aquatic environment. Detailed information is presented on the mode-of-action as well as the ecotoxicity of the most important compounds representing the three groups of MLs. This information, based on more than 360 references, is mainly provided in nine tables, presenting the effects of abamectin, ivermectin, eprinomectin, doramectin, emamectin, moxidectin, and spinosad on individual species of terrestrial and aquatic invertebrates as well as plants and algae. Since dung dwelling organisms are particularly important non-targets, as they are exposed via dung from treated animals over their whole life-cycle, the information on the effects of MLs on dung communities is compiled in an additional table. The results of this review clearly demonstrate that regarding environmental impacts many macrocyclic lactones are substances of high concern particularly with larval instars of invertebrates. Recent studies have also shown that susceptibility varies with life cycle stage and impacts can be mitigated by using MLs when these stages are not present. However information on the environmental impact of the MLs is scattered across a wide range of specialised scientific journals with research focusing mainly on ivermectin and to a lesser extent on abamectin

  16. Optical effects of different colors of artificial gingiva on ceramic crowns.

    Science.gov (United States)

    Wang, Jian; Lin, Jin; Gil, Mindy; Da Silva, John D; Wright, Robert; Ishikawa-Nagai, Shigemi

    2013-08-01

    The interaction between gingival color and the shade of ceramic restorations has never been fully studied. The purpose of this study is to investigate the optical effects of altering artificial gingival color on the ceramic crown shade in the cervical area. Thirty-one all-ceramic crowns of different shades were used in this study with six different artificial gingival colors. Using a spectrophotometer (Crystaleye(®) Olympus, Japan), we measured the shade of crowns in cervical areas with each of six different artificial gingiva. The crown color measured in the presence of pink artificial gingiva (control) was compared with the crown color with five other artificial gingiva. color difference values ΔE* were calculated and compared between the control group and test groups and the correlation of the artificial gingival color with the crown color was also assessed. Significant differences were found in the mean L* and a* values of all-ceramic crowns at the cervical regions in all six gingival color groups (pcolors of artificial gingiva generated clinically detectable shade differences in the cervical region of ceramic crowns. Copyright © 2013. Published by Elsevier Ltd.

  17. Equations for predicting diameter, height, crown width, and leaf area of San Joaquin Valley street trees

    Science.gov (United States)

    P.J. Peper; E.G. McPherson; S.M. Mori

    2001-01-01

    Although the modeling of energy-use reduction, air pollution uptake, rainfall interception, and microclimate modification associated with urban trees depends on data relating diameter at breast height (dbh) , crown height, crown diameter, and leaf area to tree age or dbh, scant information is available for common municipal tree species . I n this study , tree height ,...

  18. A Reliability Generalization Study of the Marlowe-Crowne Social Desirability Scale.

    Science.gov (United States)

    Beretvas, S, Natasha; Meyers, Jason L.; Leite, Walter L.

    2002-01-01

    Conducted a reliability generalization study of the Marlowe-Crowne Social Desirability Scale (D. Crowne and D. Marlowe, 1960). Analysis of 93 studies show that the predicted score reliability for male adolescents was 0.53, and reliability for men's responses was lower than for women's. Discusses the need for further analysis of the scale. (SLD)

  19. Crown characteristics of juvenile loblolly pine 6 years after application of thinning and fertilization

    Science.gov (United States)

    Shufang Yu; Jim L. Chambers; Zhenmin Tang; James P. Barnett

    2003-01-01

    Total foliage dry mass and leaf area at the canopy hierarchical level of needle, shoot, branch and crown were measured in 48 trees harvested from a 14-year-old loblolly pine (Pinus taeda L.) plantation, six growing seasons after thinning and fertilization treatments. In the unthinned treatment, upper crown needles were heavier and had more leaf area...

  20. An alternative method for estimating crown characteristics of urban trees using digital photographs

    Science.gov (United States)

    Matthew F. Winn; Philip A. Araman

    2012-01-01

    The USDA Forest Service Forest Inventory and Analysis (FIA) program has concluded that statewide urban forest inventories are feasible based on a series of pilot studies initiated in 2001. However, much of the tree crown data collected during inventories are based on visual inspection and therefore highly subjective. In order to objectively determine the crown...

  1. Investigating assumptions of crown archetypes for modelling LiDAR returns

    NARCIS (Netherlands)

    Calders, K.; Lewis, P.; Disney, M.; Verbesselt, J.; Herold, M.

    2013-01-01

    LiDAR has the potential to derive canopy structural information such as tree height and leaf area index (LAI), via models of the LiDAR signal. Such models often make assumptions regarding crown shape to simplify parameter retrieval and crown archetypes are typically assumed to contain a turbid

  2. Plastic collapse load of crown-hinged steel circular arches : a theoretical method

    NARCIS (Netherlands)

    Spoorenberg, R.C.; Snijder, H.H.; Hoenderkamp, J.C.D.

    2013-01-01

    For construction purposes and to avoid detrimental influences of foundation settlements arches are not always made from a single arch-rib but are built by connecting two curvilinear elements at the crown with a hinge. These arches are also known as crown-hinged arches. This paper presents an

  3. Interrelationships among light, photosynthesis and nitrogen in the crown of mature Pinus contorta ssp. latifolia

    Science.gov (United States)

    A. W. Schoettle; W. K. Smith

    1999-01-01

    Scaling leaf-level measurements to estimate carbon gain of entire leaf crowns or canopies requires an understanding of the distribution of photosynthetic capacity and corresponding light microenvironments within a crown. We have compared changes in the photosynthetic light response and nitrogen (N) content (per unit leaf area) of Pinus contorta Dougl. ssp. latifolia...

  4. Rapid crown root development confers tolerance to zinc deficiency in rice

    Directory of Open Access Journals (Sweden)

    Amrit Kaur eNanda

    2016-03-01

    Full Text Available Zinc (Zn deficiency is one of the leading nutrient disorders in rice (Oryza sativa. Many studies have identified Zn efficient rice genotypes, but causal mechanisms for Zn deficiency tolerance remain poorly understood. Here we report a detailed study of the impact of Zn deficiency on crown root development of rice genotypes, differing in their tolerance to this stress. Zn deficiency delayed crown root development and plant biomass accumulation in both Zn efficient and inefficient genotypes, with the effects being much stronger in the latter. Zn efficient genotypes had developed new crown roots as early as three days after transplanting (DAT to a Zn deficient field and that was followed by a significant increase in total biomass by 7 DAT. Zn-inefficient genotypes developed few new crown roots and did not increase biomass during the first seven days following transplanting. This correlated with Zn efficient genotypes retranslocating a higher proportion of shoot Zn to their roots, compared to Zn inefficient genotypes. These latter genotypes were furthermore not efficient in utilizing the limited Zn for root development. Histological analyses indicated no anomalies in crown tissue of Zn-efficient or inefficient genotypes that would have suggested crown root emergence was impeded. We therefore conclude that the rate of crown root initiation was differentially affected by Zn deficiency between genotypes. Rapid crown root development, following transplanting, was identified as a main causative trait for tolerance to Zn deficiency and better Zn retranslocation from shoot to root was a key attribute of Zn-efficient genotypes.

  5. Polyacrylonitrile (PAN)/crown ether composite nanofibers for the selective adsorption of cations

    NARCIS (Netherlands)

    Tas, Sinem; Kaynan, Ozge; Ozden-Yenigun, Elif; Nijmeijer, Dorothea C.

    2016-01-01

    In this study, we prepared electrospun polyacrylonitrile (PAN) nanofibers functionalized with dibenzo-18-crown-6 (DB18C6) crown ether and showed the potential of these fibers for the selective recovery of K+ from other both mono- and divalent ions in aqueous solutions. Nanofibers were characterized

  6. First report of Fusarium redolens causing crown rot of wheat (Triticum spp.) in Turkey

    Science.gov (United States)

    Fusarium crown rot, caused by a complex of Fusarium spp., is a yield-limiting disease of wheat world-wide, especially in dry Mediterranean climates. In order to identify Fusarium species associated with crown rot of wheat, a survey was conducted in summer 2013 in the major wheat growing regions of T...

  7. A semi-empirical model for predicting crown diameter of cedrela ...

    African Journals Online (AJOL)

    A semi-empirical model relating age and breast height has been developed to predict individual tree crown diameter for Cedrela odorata (L) plantation in the moist evergreen forest zones of Ghana. The model was based on field records of 269 trees, and could determine the crown cover dynamics, forecast time of canopy ...

  8. Large acceleration of a-chymotrypsin-catalyzed dipeptide formation by 18-crown-6 in organic solvents

    NARCIS (Netherlands)

    van Unen, D.J.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    The effects of 18-crown-6 on the synthesis of peptides catalyzed by α-chymotrypsin are reported. Lyophilization of the enzyme in the presence of 50 equivalents of 18-crown-6 results in a 425-fold enhanced activity when the reaction between the 2-chloroethylester of N-acetyl-L-phenylalanine and

  9. Equations relating compacted and uncompacted live crown ratio for common tree species in the South

    Science.gov (United States)

    KaDonna C. Randolph

    2010-01-01

    Species-specific equations to predict uncompacted crown ratio (UNCR) from compacted live crown ratio (CCR), tree length, and stem diameter were developed for 24 species and 12 genera in the southern United States. Using data from the US Forest Service Forest Inventory and Analysis program, nonlinear regression was used to model UNCR with a logistic function. Model...

  10. Crown releasing of red maple poles to shorten high-quality sawlog rotations

    Science.gov (United States)

    Gayne G. Erdmann; Ralph M., Jr. Peterson; Robert R. Orberg

    1985-01-01

    The effects of six crown-release treatments on growth and bole quality development of 54-year-old dominant, codominant, and intermediate red maples (Acer rubrum L.) were evaluated on a good red maple site (site index = 19.3 mat 50 years) in upper Michigan. Results showed that crown release stimulated the growth of dominants, codominants, and strong...

  11. An in-vitro investigation of the accuracy of fit of Procera and Empress crowns.

    Science.gov (United States)

    Fleming, Garry J R; Dobinson, Marie M; Landini, Gabriel; Harris, Jonathan J

    2005-09-01

    The current study aimed to investigate the accuracy of fit and the reproducibility of inner crown profile for two types of high strength ceramics, IPS Empress and Procera. Procera and Empress crowns with four different morphologies were cemented to dies using zinc phosphate dental cement. Vertical and horizontal sections were made through each of the crown/die preparations and images of the vertical sections were compared for curvature reproduction by alignment using image processing. Measurements were made on horizontal sections to determine cement layer thickness. Alignment of the crowns using image analysis identified quantifiable variations in the inner surface profile compared with the outer surface of the die. The largest differences occurred from the cusp tips to the occlusal adaptation area and differences in surface profile were less pronounced for Procera than Empress crowns. Marginal gap varied independently of ceramic or internal crown shape from 7-529 microm for Procera and 26-548 microm for Empress. IPS Empress has a superior ability to reproduce the inner surface profile of the crown morphologies investigated compared with Procera. The reduced reproduction of surface profile was associated with an increased cement thickness at the occlusal contact area that may inadvertently lead to failure of the crowns functional characteristics.

  12. Periodontal response to all-ceramic crowns (IPS Empress) in general practice.

    Science.gov (United States)

    Al-Wahadni, A M; Mansour, Y; Khader, Y

    2006-02-01

    The purpose of this study was to investigate the periodontal response to the presence of all-ceramic crowns (IPS Empress) in general practice patients. The convenience sample included 82 IPS Empress crowns placed in 64 patients. These crowns had been in place for an average of 16.27 (SD 9.26) months and ranged from 6.2 to 48.87 months at the time of clinical examination. Periodontal health status (as determined by dental plaque, gingival health status, periodontal pockets) was assessed around all crowned teeth and around matched contralateral teeth by one calibrated examiner. Periodontal indices utilized included the Plaque Index (PI), Gingival Index (GI) and pocket depth (PD) with calibrated probes graduated in millimetres. Plaque, gingival and PD values for crowned teeth were compared with those for control teeth using Wilcoxon signed-rank test for each clinical parameters. Chi-square was used to test the significance of the difference in their distribution between crowns and control teeth. Statistically, PI (0.35), GI (0.41) and mean PD scores (1.42) of IPS Empress crowned teeth compared less favourably with scores of the control teeth (0.27, 0.23 and 0.86 respectively). Teeth with IPS Empress crowns had poorer periodontal health and more clinically evident plaque than uncrowned teeth.

  13. Clinical performance of IPS-Empress 2 ceramic crowns inserted by general dental practitioners.

    Science.gov (United States)

    Mansour, Yasar F; Al-Omiri, Mahmoud K; Khader, Yousef Saleh; Al-Wahadni, Ahed

    2008-05-01

    The aim of this study was to evaluate the clinical performance of IPS-Empress 2(R) all-ceramic crowns placed by general dental practitioners. Eighty-two IPS-Empress 2 crowns placed in 64 patients (27 females and 37 males) were evaluated. These crowns had been in place for 15.2 to 57.2 months (mean 25.3 months, SD=9.3). Survival analysis was conducted using the Kaplan-Meier method. Of the 82 crowns 93.9% were rated satisfactory. In terms of the integrity of the restorations, fracture was observed in three crowns and two showed a crack upon transillumination. Five crowns were rated unsatisfactory for color match; one for marginal adaptation; and none for discoloration, secondary caries, or sensitivity. IPS-Empress 2(R) is a suitable material to fabricate all-ceramic crowns; when these all-ceramic crowns were inserted by general dental practitioners, they functioned satisfactorily with low failure rates during an observation period ranging between 15.2 to 57.2 months.

  14. In vitro evaluation of the marginal fit of different all-ceramic crowns

    Directory of Open Access Journals (Sweden)

    Munir Tolga Yucel

    2013-09-01

    Conclusion: In-Ceram all-ceramic crowns showed the largest marginal gap, and Celay crowns showed the smallest marginal gap in both die groups. The marginal discrepancies found in this study were all within the clinically acceptable standard of 120 μm.

  15. Clinical Performance of Pedo Jacket Crowns in Maxillary Anterior Primary Teeth.

    Science.gov (United States)

    Castro, Aimee; Badr, Sherine B Y; El-Badrawy, Wafa; Kulkarni, Gajanan

    2016-09-15

    To assess the clinical performance of Pedo Jacket crowns for restoration of carious primary anterior teeth. A total of 129 carious primary incisors and canines of 48 children younger than 71 months of age- were restored with Pedo Jacket crowns and resin-modified glass ionomer cementation. They were assessed for: ease of use; presence of recurrent decay; wear; partial or complete loss of the crown; color stability; gingival health; and overall clinical success over a 12-month follow-up. The patient's behavior at the restorative appointment during crown placement was also assessed. An overall clinical success of 89.5 percent of the teeth in 87.3 percent of the children was seen one year later. The crowns were easy to use, even in uncooperative children. The color stability, wear, plaque accumulation, and gingival health were acceptable. Discoloration, wear, or complete loss of the crown were found in 13.1 percent, 5.4 percent, and 7.6 percent of children, respectively. Although not statistically significant, failures were associated with poor patient cooperation at the time of crown placement, poor oral hygiene, or operator error. Pedo Jacket crowns are a viable treatment alternative for carious maxillary primary anterior teeth.

  16. Genome-Wide Association Mapping of Crown Rust Resistance in Oat Elite Germplasm.

    Science.gov (United States)

    Klos, Kathy Esvelt; Yimer, Belayneh A; Babiker, Ebrahiem M; Beattie, Aaron D; Bonman, J Michael; Carson, Martin L; Chong, James; Harrison, Stephen A; Ibrahim, Amir M H; Kolb, Frederic L; McCartney, Curt A; McMullen, Michael; Fetch, Jennifer Mitchell; Mohammadi, Mohsen; Murphy, J Paul; Tinker, Nicholas A

    2017-07-01

    Oat crown rust, caused by f. sp. , is a major constraint to oat ( L.) production in many parts of the world. In this first comprehensive multienvironment genome-wide association map of oat crown rust, we used 2972 single-nucleotide polymorphisms (SNPs) genotyped on 631 oat lines for association mapping of quantitative trait loci (QTL). Seedling reaction to crown rust in these lines was assessed as infection type (IT) with each of 10 crown rust isolates. Adult plant reaction was assessed in the field in a total of 10 location-years as percentage severity (SV) and as infection reaction (IR) in a 0-to-1 scale. Overall, 29 SNPs on 12 linkage groups were predictive of crown rust reaction in at least one experiment at a genome-wide level of statistical significance. The QTL identified here include those in regions previously shown to be linked with seedling resistance genes , , , , , and and also with adult-plant resistance and adaptation-related QTL. In addition, QTL on linkage groups Mrg03, Mrg08, and Mrg23 were identified in regions not previously associated with crown rust resistance. Evaluation of marker genotypes in a set of crown rust differential lines supported as the identity of . The SNPs with rare alleles associated with lower disease scores may be suitable for use in marker-assisted selection of oat lines for crown rust resistance. Copyright © 2017 Crop Science Society of America.

  17. Impact of a drop onto a wetted wall: description of crown formation and propagation

    Science.gov (United States)

    Roisman, I. V.; Tropea, C.

    2002-12-01

    The impact of a drop onto a liquid film with a relatively high impact velocity, leading to the formation of a crown-like ejection, is studied theoretically. The motion of a kinematic discontinuity in the liquid film on the wall due to the drop impact, the formation of the upward jet at this kinematic discontinuity and its elevation are analysed. Four main regions of the drop and film are considered: the perturbed liquid film on the wall inside the crown, the unperturbed liquid film on the wall outside the crown, the upward jet forming a crown, and the free rim bounding this jet. The theory of Yarin & Weiss (1995) for the propagation of the kinematic discontinuity is generalized here for the case of arbitrary velocity vectors in the inner and outer liquid films on the wall. Next, the mass, momentum balance and Bernoulli equations at the base of the crown are considered in order to obtain the velocity and the thickness of the jet on the wall. Furthermore, the dynamic equations of motion of the crown are developed in the Lagrangian form. An analytical solution for the crown shape is obtained in the asymptotic case of such high impact velocities that the surface tension and the viscosity effects can be neglected in comparison to inertial effects. The edge of the crown is described by the motion of a rim, formed due to the surface tension.

  18. Effects of photographic distance on tree crown atributes calculated using urbancrowns image analysis software

    Science.gov (United States)

    Mason F. Patterson; P. Eric Wiseman; Matthew F. Winn; Sang-mook Lee; Philip A. Araman

    2011-01-01

    UrbanCrowns is a software program developed by the USDA Forest Service that computes crown attributes using a side-view digital photograph and a few basic field measurements. From an operational standpoint, it is not known how well the software performs under varying photographic conditions for trees of diverse size, which could impact measurement reproducibility and...

  19. Fracture strength and failure mode of maxillary implant-supported provisional single crowns: a comparison of composite resin crowns fabricated directly over PEEK abutments and solid titanium abutments.

    Science.gov (United States)

    Santing, Hendrik Jacob; Meijer, Henny J A; Raghoebar, Gerry M; Özcan, Mutlu

    2012-12-01

    Polyetheretherketone (PEEK) temporary abutments have been recently introduced for making implant-supported provisional single crowns. Little information is available in the dental literature on the durability of provisional implant-supported restorations. The objectives of this study were to evaluate the fracture strength of implant-supported composite resin crowns on PEEK and solid titanium temporary abutments, and to analyze the failure types. Three types of provisional abutments, RN synOcta Temporary Meso Abutment (PEEK; Straumann), RN synOcta Titanium Post for Temporary Restorations (Straumann), and Temporary Abutment Engaging NobRplRP (Nobel Biocare) were used, and provisional screw-retained crowns using composite resin (Solidex) were fabricated for four different locations in the maxilla. The specimens were tested in a universal testing machine at a crosshead speed of 1 mm/minute until fracture occurred. The failure types were analyzed and further categorized as irreparable (Type 1) or reparable (Type 2). No significant difference was found between different abutment types. Only for the position of the maxillary central incisor, composite resin crowns on PEEK temporary abutments showed significantly lower (p Provisional crowns on PEEK abutments showed similar fracture strength as titanium temporary abutments except for central incisors. Maxillary right central incisor composite resin crowns on PEEK temporary abutments fractured below the mean anterior masticatory loading forces reported to be approximately 206 N. © 2010 Wiley Periodicals, Inc.

  20. Provisional Crown Dislodgement during Scuba Diving: A Case of Barotrauma

    Directory of Open Access Journals (Sweden)

    Meenal Nitin Gulve

    2013-01-01

    Full Text Available Changes in ambient pressure, for example, during flying, diving, or hyperbaric oxygen therapy, can lead to barotrauma. Although it may seem that this issue was neglected in dental education and research in recent decades, familiarity with and understanding of these facts may be of importance for dental practitioners. We report the case of a patient who experienced barotrauma involving dislodgement of a provisional crown during scuba diving. Patients who are exposed to pressure changes as a part of their jobs or hobbies and their dentists should know the causes of barotrauma. In addition, the clinician must be aware of the possible influence of pressure changes on the retention of dental components.

  1. AUTOMATIC TREE-CROWN DETECTION IN CHALLENGING SCENARIOS

    Directory of Open Access Journals (Sweden)

    D. Bulatov

    2016-06-01

    Full Text Available In this paper, a new procedure for individual tree detection and modeling is presented. The input of this procedure consists of a normalized digital surface model NDSM, and a possibly error-prone classification result. The procedure is modular so that the functionality, the advantages and the disadvantages for every single module will be explained. The most important technical contributions of the paper are: Employing watershed transformation combined with classification results, applying hotspots detectors for identifying treetops in groups of trees, and correcting NDSM by detecting and geometric reconstruction of small anomalies, such as earth walls. Two minor contributions are made up by a detailed literature research on available methods for individual tree detection and estimation of tree-crowns for clearly identified trees in order to reduce arbitrariness by assigning trees to one of the few types in the output model.

  2. Determination of radiostrontium in soil samples using a crown ether

    Energy Technology Data Exchange (ETDEWEB)

    Vajda, N; Ghods-Esphahani, A; Danesi, P R [International Atomic Energy Agency, Agency' s Laboratories, Chemistry Unit, PCI Laboratory, Seibersdorf (Austria)

    1995-07-01

    A simple and rapid method has been developed for the separation and successive determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, II. USA), oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours. (author)

  3. Determination of radiostrontium in soil samples using a crown ether

    International Nuclear Information System (INIS)

    Vajda, N.; Ghods-Esphahani, A.; Danesi, P.R.

    1995-01-01

    A simple and rapid method has been developed for the separation and successive determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, II. USA), oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours. (author)

  4. Rehabilitation of complicated crown-root fracture by invisible approach

    Directory of Open Access Journals (Sweden)

    V Leela Rani

    2016-01-01

    Full Text Available Dental trauma is one of the most common and significant problems met in all dental offices almost every day. In particular, injury to the anterior teeth is more vulnerable as it may affect the psychosocial behavior, severe emotional complications can occur leading to disturbances in their mental attitude. Cosmetic (lingual orthodontics is the recent development in the field of dentistry in the last few decades. Patients are more concerned about their appearance during the treatment and are affected by psychosocial issues because of labially placed brackets, thus leading to the evolution of lingual orthodontic appliances. In this article, we are sharing our clinical experience treating a complicated crown-root fracture using the lingual orthodontic technique.

  5. Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns.

    Science.gov (United States)

    Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko; Anić-Milošević, Sandra

    2017-06-01

    An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​: A im: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding.

  6. [Cervical adaptation of complete cast crowns of various metal alloys, with and without die spacers].

    Science.gov (United States)

    Stephano, C B; Roselino, R F; Roselino, R B; Campos, G M

    1989-01-01

    A metallic replica from a dental preparation for crown was used to make 8 class-IV stone dies. The wax patterns for the casting of the crowns were obtained in two conditions: a) from the stone die with no spacer; and b) from the stone die with an acrylic spacer. Thus, 64 metallic crowns were casted, using 4 different alloys: DURACAST (Cu-Al), NICROCAST (Ni-Cr) and DURABOND (Ni-Cr), and gold. The casted crowns were fitted in the metallic replica and measured as to the cervical discrepance of fitting. The results showed that the use of die spacers decreases the clinical discrepancies of fitting of the casted crowns (in a statistically significant level), no matter the metallic alloy employed.

  7. Zirconia crowns for rehabilitation of decayed primary incisors: an esthetic alternative.

    Science.gov (United States)

    Ashima, G; Sarabjot, K Bhatia; Gauba, K; Mittal, H C

    2014-01-01

    Esthetic management of extensively decayed primary maxillary anterior teeth requiring full coronal coverage restoration is usually challenging to the pediatric dentists especially in very young children. Many esthetic options have been tried over the years each having its own advantages, disadvantages and associated technical, functional or esthetic limitations. Zirconia crowns have provided a treatment alternative to address the esthetic concerns and ease of placement of extra-coronal restorations on primary anterior teeth. The present article presents a case where grossly decayed maxillary primary incisors were restored esthetically and functionally with ready made zirconia crowns (ZIRKIZ, HASS Corp; Korea). After endodontic treatment the decayed teeth were restored with zirconia crowns. Over a 30 months period, the crowns have demonstrated good retention and esthetic results. Dealing with esthetic needs in children with extensive loss of tooth structure, using Zirconia crowns would be practical and successful. The treatment described is simple and effective and represents a promising alternative for rehabilitation of decayed primary teeth.

  8. Enumeration of virtual libraries of combinatorial modular macrocyclic (bracelet, necklace) architectures and their linear counterparts.

    Science.gov (United States)

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

    2013-09-23

    A wide variety of cyclic molecular architectures are built of modular subunits and can be formed combinatorially. The mathematics for enumeration of such objects is well-developed yet lacks key features of importance in chemistry, such as specifying (i) the structures of individual members among a set of isomers, (ii) the distribution (i.e., relative amounts) of products, and (iii) the effect of nonequal ratios of reacting monomers on the product distribution. Here, a software program (Cyclaplex) has been developed to determine the number, identity (including isomers), and relative amounts of linear and cyclic architectures from a given number and ratio of reacting monomers. The program includes both mathematical formulas and generative algorithms for enumeration; the latter go beyond the former to provide desired molecular-relevant information and data-mining features. The program is equipped to enumerate four types of architectures: (i) linear architectures with directionality (macroscopic equivalent = electrical extension cords), (ii) linear architectures without directionality (batons), (iii) cyclic architectures with directionality (necklaces), and (iv) cyclic architectures without directionality (bracelets). The program can be applied to cyclic peptides, cycloveratrylenes, cyclens, calixarenes, cyclodextrins, crown ethers, cucurbiturils, annulenes, expanded meso-substituted porphyrin(ogen)s, and diverse supramolecular (e.g., protein) assemblies. The size of accessible architectures encompasses up to 12 modular subunits derived from 12 reacting monomers or larger architectures (e.g. 13-17 subunits) from fewer types of monomers (e.g. 2-4). A particular application concerns understanding the possible heterogeneity of (natural or biohybrid) photosynthetic light-harvesting oligomers (cyclic, linear) formed from distinct peptide subunits.

  9. Hydrolyzable tannins of tamaricaceous plants. V. Structures of monomeric-trimeric tannins and cytotoxicity of macrocyclic-type tannins isolated from Tamarix nilotica (1).

    Science.gov (United States)

    Orabi, Mohamed A A; Taniguchi, Shoko; Sakagami, Hiroshi; Yoshimura, Morio; Yoshida, Takashi; Hatano, Tsutomu

    2013-05-24

    Three new ellagitannin monomers, nilotinins M5-M7 (1-3), a dimer, nilotinin D10 (4), and a trimer, nilotinin T1 (5), together with three known dimers, hirtellin D (7) and tamarixinins B (8) and C (9), and a trimer, hirtellin T2 (6), were isolated from Tamarix nilotica dried leaves. The structures of the tannins were elucidated by intensive spectroscopic methods and chemical conversions into known tannins. The new trimer (5) is a unique macrocyclic type whose monomeric units are linked together by an isodehydrodigalloyl and two dehydrodigalloyl moieties. Additionally, dimeric and trimeric macrocyclic-type tannins isolated from T. nilotica in this study were assessed for possible cytotoxic activity against four human tumor cell lines. Tumor-selective cytotoxicities of the tested compounds were higher than those of synthetic and natural potent cytotoxic compounds, including polyphenols, and comparable with those of 5-fluorouracil and melphalan.

  10. A diversity-oriented synthesis strategy enabling the combinatorial-type variation of macrocyclic peptidomimetic scaffolds† †Electronic supplementary information (ESI) available: Experimental procedures, characterization data and details of the computational analyses. See DOI: 10.1039/c5ob00371g Click here for additional data file.

    Science.gov (United States)

    Isidro-Llobet, Albert; Hadje Georgiou, Kathy; Galloway, Warren R. J. D.; Giacomini, Elisa; Hansen, Mette R.; Méndez-Abt, Gabriela; Tan, Yaw Sing; Carro, Laura; Sore, Hannah F.

    2015-01-01

    Macrocyclic peptidomimetics are associated with a broad range of biological activities. However, despite such potentially valuable properties, the macrocyclic peptidomimetic structural class is generally considered as being poorly explored within drug discovery. This has been attributed to the lack of general methods for producing collections of macrocyclic peptidomimetics with high levels of structural, and thus shape, diversity. In particular, there is a lack of scaffold diversity in current macrocyclic peptidomimetic libraries; indeed, the efficient construction of diverse molecular scaffolds presents a formidable general challenge to the synthetic chemist. Herein we describe a new, advanced strategy for the diversity-oriented synthesis (DOS) of macrocyclic peptidomimetics that enables the combinatorial variation of molecular scaffolds (core macrocyclic ring architectures). The generality and robustness of this DOS strategy is demonstrated by the step-efficient synthesis of a structurally diverse library of over 200 macrocyclic peptidomimetic compounds, each based around a distinct molecular scaffold and isolated in milligram quantities, from readily available building-blocks. To the best of our knowledge this represents an unprecedented level of scaffold diversity in a synthetically derived library of macrocyclic peptidomimetics. Cheminformatic analysis indicated that the library compounds access regions of chemical space that are distinct from those addressed by top-selling brand-name drugs and macrocyclic natural products, illustrating the value of our DOS approach to sample regions of chemical space underexploited in current drug discovery efforts. An analysis of three-dimensional molecular shapes illustrated that the DOS library has a relatively high level of shape diversity. PMID:25778821

  11. [Finite element analysis of the maxillary central incisor with crown lengthening surgery and post-core restoration in management of crown-root fracture].

    Science.gov (United States)

    Zhen, Min; Hu, Wen-jie; Rong, Qi-guo

    2015-12-18

    To construct the finite element models of maxillary central incisor and the simulations with crown lengthening surgery and post-core restoration in management of different crown-root fracture types, to investigate the stress intensity and distributions of these models mentioned above, and to analyze the indications of crown lengthening from the point of view of mechanics. An extracted maxillary central incisor and alveolar bone plaster model were scanned by Micro-CT and dental impression scanner (3shape D700) respectively. Then the 3D finite element models of the maxillary central incisor and 9 simulations with crown lengthening surgery and post-core restoration were constructed by Mimics 10.0, Geomagic studio 9.0 and ANSYS 14.0 software. The oblique static force (100 N) was applied to the palatal surface (the junctional area of the incisal 1/3 and middle 1/3), at 45 degrees to the longitudinal axis, then the von Mises stress of dentin, periodontal ligament, alveolar bone, post and core, as well as the periodontal ligament area, were calculated. A total of 10 high-precision three-dimensional finite element models of maxillary central incisor were established. The von Mises stress of models: post>dentin>alveolar bone>core>periodontal ligament, and the von Mises stress increased linearly with the augmentation of fracture degree (besides the core). The periodontal ligament area of the crown lengthening was reduced by 12% to 33%. The von Mises stress of periodontal ligament of the B2L2c, B2L3c, B3L1c, B3L2c, B3L3c models exceeded their threshold limit value, respectively. The maxillary central incisors with the labial fracture greater than three-quarter crown length and the palatal fracture deeper than 1 mm below the alveolar crest are not the ideal indications of the crown lengthening surgery.

  12. Structure-based drug design of a highly potent CDK1,2,4,6 inhibitor with novel macrocyclic quinoxalin-2-one structure.

    Science.gov (United States)

    Kawanishi, Nobuhiko; Sugimoto, Tetsuya; Shibata, Jun; Nakamura, Kaori; Masutani, Kouta; Ikuta, Mari; Hirai, Hiroshi

    2006-10-01

    The design of a novel series of cyclin-dependent kinase (CDK) inhibitors containing a macrocyclic quinoxaline-2-one is reported. Structure-based drug design and optimization from the starting point of diarylurea 2, which we previously reported as a moderate CDK1,2,4,6 inhibitor [J. Biol.Chem.2001, 276, 27548], led to the discovery of potent CDK1,2,4,6 inhibitor that were suitable for iv administration for in vivo study.

  13. Neighbor-Directed Histidine N (s)–Alkylation: A Route to Imidazolium-Containing Phosphopeptide Macrocycles-Biopolymers | Center for Cancer Research

    Science.gov (United States)

    Our recently discovered, selective, on-resin route to N(s)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. Interestingly, these cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation.

  14. Dark and Photoinduced Cytotoxic Activity of the New Chlorophyll-a Derivatives with Oligoethylene Glycol Substituents on the Periphery of Their Macrocycles

    OpenAIRE

    Yana I. Pylina; Dmitry M. Shadrin; Oksana G. Shevchenko; Olga M. Startseva; Igor O. Velegzhaninov; Dmitry V. Belykh; Ilya O. Velegzhaninov

    2017-01-01

    In the present work, we investigated the dark and photoinduced cytotoxic activity of the new chlorophyll-a derivatives which contain the substituents of oligoethylene glycol on the periphery of their macrocycles. These compounds were tested using human cell lines to estimate their potential as photosensitizers for photodynamic therapy of cancer. It was shown that all the tested compounds have expressed photoinduced cytotoxic activity in vitro. Detailed study of the biological activity of one ...

  15. A general strategy for synthesis of cyclophane-braced peptide macrocycles via palladium-catalysed intramolecular sp3 C-H arylation

    Science.gov (United States)

    Zhang, Xuekai; Lu, Gang; Sun, Meng; Mahankali, Madhu; Ma, Yanfei; Zhang, Mingming; Hua, Wangde; Hu, Yuting; Wang, Qingbing; Chen, Jinghuo; He, Gang; Qi, Xiangbing; Shen, Weijun; Liu, Peng; Chen, Gong

    2018-05-01

    New methods capable of effecting cyclization, and forming novel three-dimensional structures while maintaining favourable physicochemical properties are needed to facilitate the development of cyclic peptide-based drugs that can engage challenging biological targets, such as protein-protein interactions. Here, we report a highly efficient and generally applicable strategy for constructing new types of peptide macrocycles using palladium-catalysed intramolecular C(sp3)-H arylation reactions. Easily accessible linear peptide precursors of simple and versatile design can be selectively cyclized at the side chains of either aromatic or modified non-aromatic amino acid units to form various cyclophane-braced peptide cycles. This strategy provides a powerful tool to address the long-standing challenge of size- and composition-dependence in peptide macrocyclization, and generates novel peptide macrocycles with uniquely buttressed backbones and distinct loop-type three-dimensional structures. Preliminary cell proliferation screening of the pilot library revealed a potent lead compound with selective cytotoxicity toward proliferative Myc-dependent cancer cell lines.

  16. Quantum chemical DFT study of the interaction between molecular oxygen and FeN₄ complexes, and effect of the macrocyclic ligand.

    Science.gov (United States)

    Silva, Adilson Luís Pereira; de Almeida, Luciano Farias; Marques, Aldaléa Lopes Brandes; Costa, Hawbertt Rocha; Tanaka, Auro Atsushi; da Silva, Albérico Borges Ferreira; de Jesus Gomes Varela, Jaldyr

    2014-03-01

    Density functional theory (DFT) was used to examine the interaction between molecular oxygen (O₂) and macrocyclic iron complexes of the type FeN₄ during the formation of FeN₄--O₂ adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O₂ was bonded to iron-tetraaza[14]annulene (FeTAA), iron-tetramethyl-tetraaza[14]annulene (FeTMTAA), iron-hexamethyl-tetraaza[14]annulene (FeHMTAA), iron dibenzotetraaza[14]annulene (FeDBTAA), and two iron-tetramethyl-dibenzotetraaza[14]annulene complexes (FeTMDBTAA1, FeTMDBTAA2). The ground state for FeN₄-O₂ adducts was the open-shell singlet. Analysis of the factors influencing the O₂ bonding process showed that different macrocyclic ligands yielded adducts with differences in O--O and Fe--O₂ bond lengths, total charge over the O₂ fragment, O--O vibrational frequency, and spin density in the O₂ fragment. A smaller energy gap between the α-HOMO of the FeN₄ complexes and the β-LUMO of O₂ increased the interaction between the complex and the O₂ molecule. The order of activity was FeDBTAA < FeTMDBTAA2 < FeTMDBTAA1 < FeTAA < FeTMTAA < FeHMTAA.

  17. Synthesis and characterization of Ni(II, Cu(II and Co(III complexes with polyamine-containing macrocycles bearing an aminoethyl pendant arm

    Directory of Open Access Journals (Sweden)

    K. S. SIDDIQI

    2004-09-01

    Full Text Available Reaction of [M(ppn2]X2 (where M = Cu(II, Ni(II, Co(II and ppn = 1,3-diaminopropane with formaldehyde and ethylenediamine in methanol results in the ready formation of a 16-membered macrocyclic complex. The complexes were characterized by elemental anlysis, IR, EPR, electronic spectral data, magnetic moments and conductance measurements. The Cu(II, Ni(II and Co(III complexes are coordinated axially with both pendant groups of the hexadentate macrocycle. These pendant donors are attached to the macrocycle by a carbon chain. The electrical conductivities of the Cu(II and Ni(II chelates indicated them to be 1:2 electrolytes whilst those of Co(III is a 1:3 electrolyte in DMSO. The EPR spectrum of the copper complex exhibited G at 3.66, which indicates a considerable exchange interaction in the complex. Spectroscopic evidence suggests that in all of the complexes the metal ion is in an octahedral environment.

  18. Modelling initial mortality of Abies religiosa in a crown fire in Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Temiño-Villota, S.; Rodríguez-Trejo, D.A.; Molina Terrén, D.M.; Ryan, K.

    2016-07-01

    Aim of the study: The objectives of this work were to determine which morphological and fire severity variables may help explain the mortality of adult Abies religiosa (Kunth) Schltdl. & Cham., to model the probability of this species after being affected by crown fire, and to obtain more elements to classify the sacred fir in terms of fire resistance. This type of studies are relevant to estimate the impact of crown fires on the climax forests that forms this species. Area of study: The burned forest was located in the southern Mexico City, borough. Material and methods: Morphological variables and fire severity indicators were collected for 335 Abies religiosa trees burned by a mixed severity fire. Logistic regression was used to analyze data and develop models that best explained tree mortality. Main results: Survival was 26.9%. The models for height (p≤0.0001), diameter at breast height (p=0.0082), crown length (p≤0.0001) and crown base height (p≤0.0001) were significant, with a negative relationship between each one of these variables and probability of mortality. The significant severity variables were lethal scorch height (p≤0.0001) and crown kill (p≤ 0.0001), which have a direct relationship with probability of mortality. Highlights: This species is moderately fire-resistant. Crown kill ≥ 70% markedly increases mortality. Silvicultural activities such as pruning, thinning and fuel management can reduce the risk of crown fires. (Author)

  19. [Comparative adaptation of crowns of selective laser melting and wax-lost-casting method].

    Science.gov (United States)

    Li, Guo-qiang; Shen, Qing-yi; Gao, Jian-hua; Wu, Xue-ying; Chen, Li; Dai, Wen-an

    2012-07-01

    To investigate the marginal adaptation of crowns fabricated by selective laser melting (SLM) and wax-lost-casting method, so as to provide an experimental basis for clinic. Co-Cr alloy full crown were fabricated by SLM and wax-lost-casting for 24 samples in each group. All crowns were cemented with zinc phosphate cement and cut along longitudinal axis by line cutting machine. The gap between crown tissue surface and die was measured by 6-point measuring method with scanning electron microscope (SEM). The marginal adaptation of crowns fabricated by SLM and wax-lost-casting were compared statistically. The gap between SLM crowns were (36.51 ± 2.94), (49.36 ± 3.31), (56.48 ± 3.35), (42.20 ± 3.60) µm, and wax-lost-casting crowns were (68.86 ± 5.41), (58.86 ± 6.10), (70.62 ± 5.79), (69.90 ± 6.00) µm. There were significant difference between two groups (P casting method and SLM method provide acceptable marginal adaptation in clinic, and the marginal adaptation of SLM is better than that of wax-lost-casting method.

  20. Modelling initial mortality of Abies religiosa in a crown fire in Mexico

    Directory of Open Access Journals (Sweden)

    Salomé Temiño-Villota

    2016-04-01

    Full Text Available Aim of study: The objectives of this work were to determine which morphological and fire severity variables may help explain the mortality of adult Abies religiosa (Kunth Schltdl. & Cham., to model the probability of this species after being affected by crown fire, and to obtain more elements to classify the sacred fir in terms of fire resistance. This type of studies are relevant to estimate the impact of crown fires on the climax forests that forms this species.Area of study: The burned forest was located in the southern Mexico City, borough.Material and methods: Morphological variables and fire severity indicators were collected for 335 Abies religiosa trees burned by a mixed severity fire. Logistic regression was used to analyze data and develop models that best explained tree mortality.Main results: Survival was 26.9%. The models for height (p≤0.0001, diameter at breast height (p=0.0082, crown length (p≤0.0001 and crown base height (p≤0.0001 were significant, with a negative relationship between each one of these variables and probability of mortality. The significant severity variables were lethal scorch height (p≤0.0001 and crown kill (p≤ 0.0001, which have a direct relationship with probability of mortality.Highlights: This species is moderately fire-resistant. Crown kill ≥ 70% markedly increases mortality. Silvicultural activities such as pruning, thinning and fuel management can reduce the risk of crown fires.

  1. The general properties of water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction systems

    International Nuclear Information System (INIS)

    Vanura, P.

    2003-01-01

    The extraction and stability constants in the system water - nitrobenzene have been collected and general rules valid for water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction system have been found. The main principles are size compatibility of ion diameter and crown cavity diameters, the flexibility of crown, the basicity of crown and the steric factor of both the ligand and the extracted ion. The extraction in the system water - mineral acid or salt polyoxyethylene compound - bis-1,2-dicarbollylcobaltate - nitrobenzene is more complicated than can be expected from usually used ion diameter - crown cavity diameter compatibility principle. The other important factors are the basicity and the deformability of crown, steric aspect and the angles of bonds of extracted ion. The binuclear 'sandwich' complexes with H + ion and Sr 2+ or Ba 2+ ions have been proved for dibenzo-18-crown-6 (DB18C6). On the other hand, only SrL 2 and BaL 2 (L = 15C5) complexes are formed in nitrobenzene saturated with water. The addition of polyoxyethylene compound usually increases the distribution ratio of alkali earth metal ions and the selectivity of its mutual separation. (authors)

  2. Effect of electrostatic interaction on thermochemical behavior of 12-crown-4 ether in various polar solvents

    International Nuclear Information System (INIS)

    Barannikov, Vladimir P.; Guseynov, Sabir S.; Vyugin, Anatoliy I.

    2010-01-01

    The enthalpies of solution of 12-crown-4 ether have been measured in chloroform, ethyl acetate, acetone, pyridine, acetonitrile and methanol at 298.15 K. The values of enthalpy of solvation and solute-solvent interaction were determined from the obtained results and similar literature data for 12-crown-4 in solvents of various polarities. It was shown that the certain correlation is observed between the enthalpy of solute-solvent interaction and the squared dipole moment of the solvent molecules for solutions in tetrachlormethane, ethyl acetate, pyridine, acetonitrile, DMF, DMSO and propylene carbonate. This means that the electrostatic interaction of 12-crown-4 with polar solvent molecules contributes significantly to the exothermic effect of solvation. The understated negative value was found for the enthalpy of interaction of 12-crown-4 with acetone that can be connected with domination of low polar conformer of the crown ether in acetone medium. The most negative values of enthalpy of solvation are observed for solutions in chloroform and water because of hydrogen bonding between O-atoms of crown ether and molecules of the indicated solvents. This effect is not observed for methanol. The negative coefficient of pairwise solute-solute interaction in methanol indicates that the effects of solvophobic solute-solute interaction and H-bonding of the ether molecule with chain associates of methanol are not evinced in the thermochemical behavior of 12-crown-4.

  3. [Comparative study of microleakage by using different finished lines in selective laser melting metal crowns].

    Science.gov (United States)

    Peng, Yan; Zhong, Qun; Wu, Xue-Ying; Weng, Jia-Wei

    2016-12-01

    To evaluate microleakage of SLM Co -Cr alloy metal crown with two types finished line (chamfer and shoulder), compared with conventional fabrication of Co -Cr alloy metal crowns. Thirty healthy non-carious human molars were selected and randomly assigned to 3 groups, 10 in each. Teeth in group A and C received a chamfer finish line preparation, whereas teeth in group C received a shoulder finish line. Conventional Co -Cr alloy metal crowns were fabricated for group A when SLM metal crowns were made for group B and group C. Glass ionomer was applied for bonding. After 5000 thermocycles ranging from 5degrees centigrade to 55degrees centigrade,all the specimens were evaluated by dye penetration and then microleakage was examined under light microscope. The data were analyzed statistically with SPSS 20.0 software package. Microleakage in group A was significantly higher than the other two groups, group B and group C showed no significant difference in microleakage while microleakage in group B was higher than that in group C. Microleakage of SLM metal crowns was significantly less than that of conventional Co-Cr alloy metal crowns; chamfer finish line designs was recommended for SLM metal crowns in consideration of reducing microleakage and protecting tooth.

  4. Comparative in vitro evaluation of CAD/CAM vs conventional provisional crowns

    Directory of Open Access Journals (Sweden)

    Adil Othman ABDULLAH

    Full Text Available ABSTRACT Objective This study compared the marginal gap, internal fit, fracture strength, and mode of fracture of CAD/CAM provisional crowns with that of direct provisional crowns. Material and Methods An upper right first premolar phantom tooth was prepared for full ceramic crown following tooth preparation guidelines. The materials tested were: VITA CAD-Temp®, Polyetheretherketone “PEEK”, Telio CAD-Temp, and Protemp™4 (control group. The crowns were divided into four groups (n=10, Group1: VITA CAD-Temp®, Group 2: PEEK, Group 3: Telio CAD-Temp, and Group 4: Protemp™4. Each crown was investigated for marginal and internal fit, fracture strength, and mode of fracture. Statistical analysis was performed using GraphPad Prism software version 6.0. Results The average marginal gap was: VITA CAD-Temp® 60.61 (±9.99 µm, PEEK 46.75 (±8.26 µm, Telio CAD-Temp 56.10 (±5.65 µm, and Protemp™4 193.07(±35.96 µm (P0.05. Conclusions CAD/CAM fabricated provisional crowns demonstrated superior fit and better strength than direct provisional crowns.

  5. Evaluation of different sterilization and disinfection methods on commercially made preformed crowns.

    Science.gov (United States)

    Yilmaz, Y; Guler, C

    2008-12-01

    The aim of this study was to evaluate the changes caused by different sterilization or disinfection methods on the vestibular surface of four commercially made preformed crowns using stereomicroscopy and scanning electron microscopy (SEM). Preformed crowns (NuSmile Primary Anterior Crown (NSC), Kinder Krowns (KK), Pedo Pearls (PP) and polycarbonate crowns (PC)) were sterilized and/or disinfected by one of the following techniques: no sterilization or disinfection (G1 control group); steam autoclaving at 134 degrees C (30 psi) for 4 min (G2); steam autoclaving at 134 degrees C (30 psi) for 12 min (G3); steam autoclaving at 121 degrees C (15 psi) for 30 min (G4); and ultrasonication in a bath containing 4% Lysetol AF for 5 min at room temperature (chemical disinfection) (G5). Scanning electron micrographs of the crowns were taken before and after their sterilization or disinfection. The changes on the vestibular surface were then scored for the presence or absence of crazing, contour alteration, fracturing, and vestibular surface changes. The data were analyzed statistically using the chi-square test. No changes were observed before and after sterilization or disinfection in the stereomicroscopic evaluation of the vestibular surface of the crowns. However, all methods in which steam autoclaving was used to sterilize the crowns caused significant (P < 0.05) crazing and contour alterations of the vestibular surface of the crowns when they were examined by SEM. Chemical disinfection using an aldehyde-free disinfectant is the preferred method of disinfection for crowns that have been used previously in other dental patients.

  6. Crown and crown-root fractures: an evaluation of the treatment plans for management proposed by 154 specialists in restorative dentistry.

    Science.gov (United States)

    de Castro, Mara Antonio Monteiro; Poi, Wilson Roberto; de Castro, José Carlos Monteiro; Panzarini, Sônia Regina; Sonoda, Celso Koogi; Trevisan, Carolina Lunardelli; Luvizuto, Eloá Rodrigues

    2010-06-01

    Traumatic tooth injuries involve function and aesthetics and cause damage that range from minimal enamel loss to complex fractures involving the pulp tissue and even loss of the tooth crown. Technical knowledge and clinical experience are essential to establish an accurate diagnosis and provide a rational treatment. The purpose of this study was to evaluate the knowledge of Restorative Dentistry specialists about the management of crown and crown-root fractures based on treatment plans proposed by these professionals for these cases. A descriptive questionnaire was mailed to 245 Restorative Dentistry specialists with questions referring to their professional profile and the treatment plans they would propose for the management of crown and crow-root fractures resulting from dental trauma. One hundred and fifty-four questionnaires were returned properly filled. The data were subjected to descriptive statistics and the chi-square test was used to determine the frequency and the level of the significance among the variables. The analysis of data showed that in spite of having a specialist title, all interviewees had great difficulty in planning the treatments. As much as 42.8% of the participants were unable to treat all types of dental trauma. Complicated and uncomplicated crown-root fractures posed the greatest difficulties for the dentists to establish adequate treatment plans because these fractures require multidisciplinary knowledge and approach for a correct case planning and prognosis.

  7. [An in vitro study of the fracture strength of tooth preparations for Empress 2 veneers and crowns and mandibular incisors restored with Empress 2 veneers and crowns].

    Science.gov (United States)

    Wei, Xue; Li, Yan

    2009-12-01

    To compare the fracture resistance of mandibular incisors' preparations for veneers and crowns, mandibular incisors restored with Empress 2 veneers and crowns. 50 human mandibular incisors were randomly divided into five groups. Each group consisted of ten teeth and the treatment obtained as follows: A, tooth preparations for veneers; B, tooth preparations for crowns; C, teeth restored with veneers; D, teeth restored with crowns; E, untreated group. The teeth received standardized preparation and the restorations were manufactured with Empress 2 system and cemented with resin luting agent. The fracture resistances of teeth were measured by Instron universal testing machine and statistically analyzed with one-way ANOVA. The fracture resistances of A, B, C, D, E were (576.11 +/- 91.53), (204.13 +/- 85.88), (451.50 +/- 116.81), (386.16 +/- 117.75) and (566.05 +/- 121.37) N, respectively. The statistical analysis demonstrated significant differences between five groups. There were no significant differences between group A and E, group C and D. Tooth preparations for veneers did not significantly reduce the fracture resistance of mandibular incisor. The fracture resistance of teeth restored with Empress 2 veneers and crowns did not significantly differ from each other.

  8. Online recovery of radiocesium from soil, cellulose and plant samples by supercritical fluid extraction employing crown ethers and calix-crown derivatives as extractants

    International Nuclear Information System (INIS)

    Kanekar, A.S.; Pathak, P.N.; Mohapatra, P.K.

    2014-01-01

    Two crown ethers (CEs) viz. dibenzo18crown6, and dibenzo12crown7 and three calix-crown derivatives viz. (octyloxy)calix[4]arene-mono-crown-6 (CMC), calix[4]arene-bis(o-benzocrown-6) (CBC), and calix[4]arene-bis(naphthocrown-6) (CNC) were evaluated for the recovery of 137 Cs from synthetic soil, cellulose (tissue paper), and plant samples by supercritical fluid extraction (SFE) route. CEs showed poor extraction of 137 Cs from soil matrix. SFE experiments using 1 × 10 -3 M solutions of CMC, CBC and CNC in acetonitrile at 3 M HNO 3 as modifiers displayed better extraction of 137 Cs, viz. 21(±2) % (CMC), 16.5(±3) % (CBC), and 4(±1) % (CNC). It was not possible to recover 137 Cs quantitatively from soil matrix. The inefficient extraction of 137 Cs from soil matrix was attributed to its incorporation into the interstitial sites. Experiments on tissue papers using CMC showed near quantitative 137 Cs recovery. On the other hand, recovery from plant samples varied between 50(±5) % (for stems) and 75(±5) % (for leaves). (author)

  9. CROWN-LEVEL TREE SPECIES CLASSIFICATION USING INTEGRATED AIRBORNE HYPERSPECTRAL AND LIDAR REMOTE SENSING DATA

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2018-05-01

    Full Text Available Mapping tree species is essential for sustainable planning as well as to improve our understanding of the role of different trees as different ecological service. However, crown-level tree species automatic classification is a challenging task due to the spectral similarity among diversified tree species, fine-scale spatial variation, shadow, and underlying objects within a crown. Advanced remote sensing data such as airborne Light Detection and Ranging (LiDAR and hyperspectral imagery offer a great potential opportunity to derive crown spectral, structure and canopy physiological information at the individual crown scale, which can be useful for mapping tree species. In this paper, an innovative approach was developed for tree species classification at the crown level. The method utilized LiDAR data for individual tree crown delineation and morphological structure extraction, and Compact Airborne Spectrographic Imager (CASI hyperspectral imagery for pure crown-scale spectral extraction. Specifically, four steps were include: 1 A weighted mean filtering method was developed to improve the accuracy of the smoothed Canopy Height Model (CHM derived from LiDAR data; 2 The marker-controlled watershed segmentation algorithm was, therefore, also employed to delineate the tree-level canopy from the CHM image in this study, and then individual tree height and tree crown were calculated according to the delineated crown; 3 Spectral features within 3 × 3 neighborhood regions centered on the treetops detected by the treetop detection algorithm were derived from the spectrally normalized CASI imagery; 4 The shape characteristics related to their crown diameters and heights were established, and different crown-level tree species were classified using the combination of spectral and shape characteristics. Analysis of results suggests that the developed classification strategy in this paper (OA = 85.12 %, Kc = 0.90 performed better than Li

  10. Crown-Level Tree Species Classification Using Integrated Airborne Hyperspectral and LIDAR Remote Sensing Data

    Science.gov (United States)

    Wang, Z.; Wu, J.; Wang, Y.; Kong, X.; Bao, H.; Ni, Y.; Ma, L.; Jin, J.

    2018-05-01

    Mapping tree species is essential for sustainable planning as well as to improve our understanding of the role of different trees as different ecological service. However, crown-level tree species automatic classification is a challenging task due to the spectral similarity among diversified tree species, fine-scale spatial variation, shadow, and underlying objects within a crown. Advanced remote sensing data such as airborne Light Detection and Ranging (LiDAR) and hyperspectral imagery offer a great potential opportunity to derive crown spectral, structure and canopy physiological information at the individual crown scale, which can be useful for mapping tree species. In this paper, an innovative approach was developed for tree species classification at the crown level. The method utilized LiDAR data for individual tree crown delineation and morphological structure extraction, and Compact Airborne Spectrographic Imager (CASI) hyperspectral imagery for pure crown-scale spectral extraction. Specifically, four steps were include: 1) A weighted mean filtering method was developed to improve the accuracy of the smoothed Canopy Height Model (CHM) derived from LiDAR data; 2) The marker-controlled watershed segmentation algorithm was, therefore, also employed to delineate the tree-level canopy from the CHM image in this study, and then individual tree height and tree crown were calculated according to the delineated crown; 3) Spectral features within 3 × 3 neighborhood regions centered on the treetops detected by the treetop detection algorithm were derived from the spectrally normalized CASI imagery; 4) The shape characteristics related to their crown diameters and heights were established, and different crown-level tree species were classified using the combination of spectral and shape characteristics. Analysis of results suggests that the developed classification strategy in this paper (OA = 85.12 %, Kc = 0.90) performed better than LiDAR-metrics method (OA = 79

  11. Complexation between Methyl Viologen (Paraquat) Bis(Hexafluorophosphate) and Dibenzo[24]Crown-8 Revisited

    DEFF Research Database (Denmark)

    Gasa, Travis B.; Spruell, Jason M.; Dichtel, William R.

    2009-01-01

    Paraquat bis(hexafluorophosphate) undergoes stepwise dissociation in acetone. All three species - the neutral molecule, and the mono- and dications - are represented significantly under the experimental conditions typically used in host-guest binding studies. Paraquat forms at least four host...... toward dibenzo[24]crown-8. Thus, the relative abundance of neutral, singly, and doubly charged pseudorotaxanes is identical to the relative abundance of neutral, singly, and doubly charged paraquat unbound with respect to the crown ether in acetone. In the specific case of paraquat/dibenzo[24]crown-8...

  12. A comparison of the marginal fit of In-Ceram, IPS Empress, and Procera crowns.

    Science.gov (United States)

    Sulaiman, F; Chai, J; Jameson, L M; Wozniak, W T

    1997-01-01

    The in vitro marginal fit of three all-ceramic crown systems (In-Ceram, Procera, and IPS Empress) was compared. All crown systems were significantly different from each other at P = 0.05. In-Ceram exhibited the greatest marginal discrepancy (161 microns), followed by Procera (83 microns), and IPS Empress (63 microns). There were no significant differences among the various stages of the crown fabrication: core fabrication, porcelain veneering, and glazing. The facial and lingual margins exhibited significantly larger marginal discrepancies than the mesial and distal margins.

  13. Evaluation of various Crown ethers for the supercritical fluid extraction of uranium from nitric acid medium

    International Nuclear Information System (INIS)

    Kumar, Pradeep; Rao, Ankita; Ramakumar, K.L.

    2009-01-01

    Various crowns have been evaluated for supercritical fluid extraction of uranium from nitric acid medium employing HPFOA as counter ion. Uranium extraction efficiency was found to be influenced by cavity size of crown ether and nature of substituents. Complexation tendency of UO 2 2+ increases with increasing cavity size of crown ether. Electron withdrawing substituents decreased the extraction efficiency which could be attributed to decrease in the basicity of four oxygen atoms and hence their bonding ability. Whereas electron donating substituents increased the efficiency due to increases in basicity of oxygen atoms and hence in increase in bonding ability. (author)

  14. Management of complicated crown-root fracture in central incisors using intentional replantation with 180° rotation: A case report

    Directory of Open Access Journals (Sweden)

    Reyhaneh Faghihian

    2017-01-01

    Full Text Available Introduction: Complicated crown-root fractures are rare and their treatment is complex. Numerous methods such as crown lengthening and orthodontic or surgical extrusion have been described for the treatment of crown-root fracture. The aim of this study was to report managing complicated crown-root fracture using intentional replantation with 180° rotation. Case report: This case report demonstrates successful management of complicated crown-root fracture in central incisor of a 10-year-old boy using intentional replantation with 180° rotation. Discussion: At 18-month follow-up, the replanted tooth revealed normal function with no obvious resorption.

  15. Investigation of iron(III) complex with crown-porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Pankratov, Denis A., E-mail: pankratov@radio.chem.msu.ru; Dolzhenko, Vladimir D. [Lomonosov Moscow State University (Russian Federation); Stukan, Reonald A. [Semenov Institute of Chemical Physics, Russian Academy of Sciences (Russian Federation); Al Ansari, Yana F.; Savinkina, Elena V. [Lomonosov Moscow State Academy of Fine Chemical Technology (Russian Federation); Kiselev, Yury M. [Lomonosov Moscow State University (Russian Federation)

    2013-08-15

    Iron complex of 5-(4-(((4 Prime -hydroxy-benzo-15-crown-5)-5 Prime -yl)diazo)phenyl)-10,15, 20-triphenylporphyrin was investigated by {sup 57}Fe Moessbauer spectroscopy and EPR. Two Fe sites were identified; they give two differing signals, doublet and wide absorption in a large velocity interval. EPR spectra of solutions of the complex in chloroform at room temperature also show two signals with g = 2.064, A{sub Fe} = 0.032 cm{sup - 1}; g = 2.015, A{sub Fe} = 0.0034 cm{sup - 1}. The doublet asymmetry is studied vs. temperature and normal angle to the sample plane and gamma-beam. The isomer shift {delta} in the doublet varies from 0.25 to 0.41 mm/s in the 360-5 K temperature range, whereas quadruple splitting value is constant, {Delta} {approx} 0.65 mm/s. The relax absorption may be described as a wide singlet ({delta} = 0.30- 0.44 mm/s and {Gamma} = 2.83-3.38 mm/s); its relative area strongly depends on temperature. According to {delta}, both signals are assigned to Fe(III)

  16. The Role of the British Crown on Security Issues

    Directory of Open Access Journals (Sweden)

    Behar Selimi

    2016-07-01

    Full Text Available United Kingdom is a limited parliamentary monarchy, in which state sovereignty is exercised jointly by two basic political institutions: Royal Crown and Parliament. The credit for a successful political co-governance of these institutions, which are simultaneously bearers of popular sovereignty, are usually addressed to the Queen's lack of executive power to exercise power alone and hence all the restraint in the race for primate of governance. It goes even further considering that the Queen is quite weak and has only ceremonial functions, which do not disturb the Parliament. However, a careful researcher may notice that the Queen continues to affect the British Government in general and in particular on defence issues. Declassification of communication between Prince Charles and the Government in 2013, pointed out a continuing impact of the Queen and her son on many political issues, including those of defence and security. Since Britain has no codified constitution in a single document, it is not easy to determine the real power and competences of the Queen. It is even more difficult, because customary law and precedent prevail. Therefore, the real definition of the role of the Queen in general in the British Government, can be done by studying the culture, structure and constitutional practice. On their basis I will try to determine the real impact of the Queen in matters of defence and security, whether through her prerogatives in relation to the Government and Parliament, or through moral and informal influence in relation to the Prime Minister and particular ministers.

  17. Unidirectional infiltration method to produce crown for dental prosthesis application

    International Nuclear Information System (INIS)

    Pontes, F.H.D.; Taguchi, S.P.; Machado, J.P.B.; Santos, C.

    2009-01-01

    Alumina ceramics have been used in dental prosthesis because it is inert, presents higher corrosion and shear resistance when compared to metals, excellent aesthetic, and mechanical resistance. In this work it was produced an infrastructure material for applications in dental crowns, obtained by glass infiltration in alumina preform. Various oxides, among that, rare-earth oxide produced by Xenotime, were melted at 1450 deg C and heat treatment at 700 deg C to obtain the glass (REglass). The alumina was pre-sintered at 1100 deg C cut and machined to predetermine format (unidirectional indirect infiltration) and finally conducted to infiltration test. The alumina was characterized by porosity (Hg-porosity and density) and microstructure (SEM). The glass wettability in alumina was determined as function of temperature, and the contact angle presented a low value (θ<90 deg), showing that glass can be infiltrated spontaneously in alumina. The infiltration test was conducted at glass melting temperature, during 30, 60, 180, 360 minutes. After infiltration, the samples were cut in longitudinal section, ground and polished, and analyzed by XRD (crystalline phases), SEM (microstructure) and EDS (composition).The REglass presents higher infiltration height when compared to current processes (direct infiltration), and homogeneous microstructure, showing that it is a promising method used by prosthetics and dentists. (author)

  18. Archaeobatrachian paraphyly and pangaean diversification of crown-group frogs.

    Science.gov (United States)

    Roelants, Kim; Bossuyt, Franky

    2005-02-01

    Current models for the early diversification of living frogs inferred from morphological, ontogenetic, or DNA sequence data invoke very different scenarios of character evolution and biogeography. To explore central controversies on the phylogeny of Anura, we analyzed nearly 4000 base pairs of mitochondrial and nuclear DNA for the major frog lineages. Likelihood-based analyses of this data set are congruent with morphological evidence in supporting a paraphyletic arrangement of archaeobatrachian frogs, with an (Ascaphus + Leiopelma) clade as the sister-group of all other living anurans. The stability of this outcome is reinforced by screening for phylogenetic bias resulting from site-specific rate variation, homoplasy, or the obligatory use of distantly related outgroups. Twenty-one alternative branching and rooting hypotheses were evaluated using a nonparametric multicomparison test and parametric bootstrapping. Relaxed molecular clock estimates situate the emergence of crown-group anurans in the Triassic, approximately 55 million years prior to their first appearance in the fossil record. The existence of at least four extant frog lineages on the supercontinent Pangaea before its breakup gains support from the estimation that three early splits between Laurasia- and Gondwana-associated families coincide with the initial rifting of these landmasses. This observation outlines the potential significance of this breakup event in the formation of separate Mesozoic faunal assemblages in both hemispheres.

  19. [Study on color of thermosetting resin for veneer crown].

    Science.gov (United States)

    Kamitomai, H

    1989-02-01

    Based on the viewpoint that stresses the importance of achieving natural colors and forms for veneer crown, four representative kinds of thermosetting resins were investigated colorimetrically in an attempt to clarify the relationship between the thickness and color of resins in opaque, dentin and enamel colors respectively. A spectrophotometer was used to measure the colors, the CIE colorimetric system employed to show the readings, and the CIE 1964 U*V*W* space was utilized to indicate the color differences, with the following results. 1. In the case of dentin, certain specific colors were observed for thickness of 1.3 to 1.8 mm when used alone, but when applied over opaque the range was 0.2 to 0.5 mm lower than when used alone. 2. Enamel resins were grouped into two types according to different color groups, one group similar to achromatic color with low limpidity and the other similar to the dentin color with high limpidity. The former type became more grayer with an increase in thickness when applied over dentin. The latter type showed no difference in color even when the thickness increased. This study has shown that the facing color results vary depending on the color properties of the different resins used. Therefore, it is advisable that careful consideration be given to these differencies in order to achieve the intended color facing.

  20. Crown ethers and phase transfer catalysis in polymer science

    CERN Document Server

    Carraher, Charles

    1984-01-01

    Phase transfer catalysis or interfacial catalysis is a syn­ thetic technique involving transport of an organic or inorganic salt from a solid or aqueous phase into an organic liquid where reaction with an organic-soluble substrate takes place. Over the past 15 years there has been an enormous amount of effort invested in the development of this technique in organic synthe­ sis. Several books and numerous review articles have appeared summarizing applications in which low molecular weight catalysts are employed. These generally include either crown ethers or onium salts of various kinds. While the term phase transfer catalysis is relatively new, the concept of using a phasetrans­ fer agent (PTA) is much older~ Both Schnell and Morgan employed such catalysts in synthesis of polymeric species in the early 1950's. Present developments are really extensions of these early applications. It has only been within the last several years that the use of phase transfer processes have been employed in polymer synthesis...

  1. Unidirectional infiltration method to produce crown for dental prosthesis application

    Energy Technology Data Exchange (ETDEWEB)

    Pontes, F.H.D.; Taguchi, S.P. [Universidade de Sao Paulo (EEL/DEMAR/USP), Lorena, SP (Brazil). Escola de Engenharia; Borges Junior, L.A. [Centro Universitario de Volta Redonda, RJ (Brazil); Machado, J.P.B. [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil); Santos, C. [ProtMat Materiais Avancados, Guaratingueta, SP (Brazil)

    2009-07-01

    Alumina ceramics have been used in dental prosthesis because it is inert, presents higher corrosion and shear resistance when compared to metals, excellent aesthetic, and mechanical resistance. In this work it was produced an infrastructure material for applications in dental crowns, obtained by glass infiltration in alumina preform. Various oxides, among that, rare-earth oxide produced by Xenotime, were melted at 1450 deg C and heat treatment at 700 deg C to obtain the glass (REglass). The alumina was pre-sintered at 1100 deg C cut and machined to predetermine format (unidirectional indirect infiltration) and finally conducted to infiltration test. The alumina was characterized by porosity (Hg-porosity and density) and microstructure (SEM). The glass wettability in alumina was determined as function of temperature, and the contact angle presented a low value (θ<90 deg), showing that glass can be infiltrated spontaneously in alumina. The infiltration test was conducted at glass melting temperature, during 30, 60, 180, 360 minutes. After infiltration, the samples were cut in longitudinal section, ground and polished, and analyzed by XRD (crystalline phases), SEM (microstructure) and EDS (composition).The REglass presents higher infiltration height when compared to current processes (direct infiltration), and homogeneous microstructure, showing that it is a promising method used by prosthetics and dentists. (author)

  2. Eocene diversification of crown group rails (Aves: Gruiformes: Rallidae).

    Science.gov (United States)

    García-R, Juan C; Gibb, Gillian C; Trewick, Steve A

    2014-01-01

    Central to our understanding of the timing of bird evolution is debate about an apparent conflict between fossil and molecular data. A deep age for higher level taxa within Neoaves is evident from molecular analyses but much remains to be learned about the age of diversification in modern bird families and their evolutionary ecology. In order to better understand the timing and pattern of diversification within the family Rallidae we used a relaxed molecular clock, fossil calibrations, and complete mitochondrial genomes from a range of rallid species analysed in a Bayesian framework. The estimated time of origin of Rallidae is Eocene, about 40.5 Mya, with evidence of intrafamiliar diversification from the Late Eocene to the Miocene. This timing is older than previously suggested for crown group Rallidae, but fossil calibrations, extent of taxon sampling and substantial sequence data give it credence. We note that fossils of Eocene age tentatively assigned to Rallidae are consistent with our findings. Compared to available studies of other bird lineages, the rail clade is old and supports an inference of deep ancestry of ground-dwelling habits among Neoaves.

  3. Clinical evaluation of all-ceramic crowns fabricated from intraoral digital impressions based on the principle of active wavefront sampling.

    Science.gov (United States)

    Syrek, Andreas; Reich, Gunnar; Ranftl, Dieter; Klein, Christoph; Cerny, Barbara; Brodesser, Jutta

    2010-07-01

    The aim of the present study was to compare the fit of all-ceramic crowns fabricated from intraoral digital impressions with the fit of all-ceramic crowns fabricated from silicone impressions. Twenty patients agreed to take part in the study to receive two Lava crowns each for the same preparation. One crown was fabricated from intraoral scans using the Lava Chairside Oral Scanner (Lava C.O.S.), and the other crown from a two-step silicone impression. Prior to cementation the fit of both crowns was clinically evaluated by two calibrated and blinded examiners; the marginal fit was also scored from replicas. Data from the replica scores were analysed by Anderson-Darling test, Levene's test and Mann-Whitney test. All tests were performed with alpha-level of 0.05. Median marginal gap in the conventional impression group was 71microm (Q1:45microm; Q3:98microm), and in the digital impression group 49microm (Q1:32microm; Q3:65microm). Mann-Whitney test revealed a significant difference between the groups (pdigitally fabricated crowns. 1. Crowns from intraoral scans revealed significantly better marginal fit than crowns from silicone impressions. 2. Marginal discrepancies in both groups were within the limits of clinical acceptability. 3. Crowns from intraoral scans tended to show better interproximal contact area quality. 4. Crowns from both groups performed equally well with regard to occlusion. Copyright 2010 Elsevier Ltd. All rights reserved.

  4. 1,3-Alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6 as an extraordinarily strong receptor for the univalent silver cation

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Dybal, Jiří; Vaňura, P.

    2017-01-01

    Roč. 148, č. 8 (2017), s. 1379-1383 ISSN 0026-9247 Institutional support: RVO:61389013 Keywords : calixarenes * macrocycles * complexation Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 1.282, year: 2016

  5. Crown ether complexes of lanthanoid and actinoid elements. Crystal and molecular structure of Nd(NO/sub 3/)/sub 3/(18-crown-6)

    Energy Technology Data Exchange (ETDEWEB)

    Bombieri, G; De Paoli, G; Benetollo, F [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Cassol, A [Padua Univ. (Italy)

    1980-01-01

    Nd(NO/sub 3/)/sub 3/.18-Crown-6 crystallizes in the orthorhombic system, space group Pbca with eight molecules in a cell of dimensions a = 15.512(9), b = 21.662(1), c = 12.141(6) A. The structure has been determined by Patterson heavy-atom methods and refined by full-matrix least squares to R = 0.038. The neodymium atom is coordinated by 6 oxygen atoms of the 18-crown-6 unit and by three bidentate nitrate groups; one on the more hindered side of the ring and two on the opposite side.

  6. In vitro analysis of the marginal adaptation and discrepancy of stainless steel crowns

    Science.gov (United States)

    Mulder, Riaan; Medhat, Rasha; Mohamed, Nadia

    2018-01-01

    Abstract Aim: The purpose of the study was to assess the marginal adaptation and discrepancy of SSC’s. Differences in adaptation and discrepancy between the four surfaces (mesial, lingual, distal, and buccal) were evaluated. Methods: The placement of stainless steel crowns were completed on a phantom head in accordance with the clinical technique. The ideal tooth preparation was made and this ‘master tooth’ duplicated to achieve a sample size of 15. The stainless steel crowns were placed, trimmed, and cemented as per the clinical technique. The cemented stainless crowns were analyzed under 100× stereomicroscope magnification. The marginal adaptation and discrepancy of each specimen was measured every 2 µm. Results: All the specimens showed marginal adaptation and discrepancy. The lingual margin had a significantly better adaptation (p steel crown adaptation and discrepancy is an essential clinical step. PMID:29536024

  7. [Effects of habitat fragmentation on nesting site selection of red-crowned crane].

    Science.gov (United States)

    Wan, Dongmei; Gao, Wei; Wang, Qiuyu; Wang, Haitao; Liu, Mingyu

    2002-05-01

    During April and May of 1985, 1995 and 1998, red-crowned crane's nesting and variation of breeding population quantities in Shuangtaihekou National Natural Reserve in Liaoning, and also the habitat fragmentation there were investigated. Associated with previous data of the reserve, red-crowned crane's nesting habitat had been seriously fragmentated into 91 patches from one integrated reed wetland. The area of the smallest patch was 0.37 km2, and the minimum distance of two nests was 304 m. Compared with records of previous data, the minimum area of nesting habitat reduced by 0.72 km2. However, the breeding population quantities of red-crowned crane had maintained at about 30 pairs for a long period. The red-crowned crane adapted to the changed environment by the ecological adaptation strategy of reducing area of nesting habitat.

  8. Experiments on the breakup of drop-impact crowns by Marangoni holes

    KAUST Repository

    Aljedaani, Abdulrahman Barakat; Wang, Chunliang; Jetly, Aditya; Thoroddsen, Sigurdur T

    2018-01-01

    We investigate experimentally the breakup of the Edgerton crown due to Marangoni instability when a highly viscous drop impacts on a thin film of lower-viscosity liquid, which also has different surface tension than the drop liquid. The presence

  9. [Computer aided design and manufacture of the porcelain fused to metal crown].

    Science.gov (United States)

    Nie, Xin; Cheng, Xiaosheng; Dai, Ning; Yu, Qing; Hao, Guodong; Sun, Quanping

    2009-04-01

    In order to satisfy the current demand for fast and high-quality prosthodontics, we have carried out a research in the fabrication process of the porcelain fused to metal crown on molar with CAD/CAM technology. Firstly, we get the data of the surface mesh on preparation teeth through a 3D-optical grating measuring system. Then, we reconstruct the 3D-model crown with the computer-aided design software which was developed by ourselves. Finally, with the 3D-model data, we produce a metallic crown on a high-speed CNC carving machine. The result has proved that the metallic crown can match the preparation teeth ideally. The fabrication process is reliable and efficient, and the restoration is precise and steady in quality.

  10. Telescopic crowns as attachments for implant supported restorations: a case series.

    Science.gov (United States)

    Hoffmann, Oliver; Beaumont, Christian; Tatakis, Dimitris N; Zafiropoulos, Gregory-George

    2006-01-01

    The use of dental implants to support mandibular or maxillary overdentures is a widely used treatment modality. Advantages are an increase in retention, an increase in chewing ability, and easy access for oral hygiene procedures. While telescopic and conical crowns have been used for decades to connect natural teeth to overdentures, not many cases have been reported in the literature of telescopic crowns placed on implants to support overdentures. This article describes 7 patients with overdentures supported by telescopic crowns who received 65 implants (ITI Straumann). The cases presented in this report have been in function for up to 4.5 years. During that time no adverse events were reported. The use of telescopic crowns as attachments for implant-supported overdentures may be a viable treatment option.

  11. Influence of different post core materials on the color of Empress 2 full ceramic crowns.

    Science.gov (United States)

    Ge, Jing; Wang, Xin-zhi; Feng, Hai-lan

    2006-10-20

    For esthetic consideration, dentin color post core materials were normally used for all-ceramic crown restorations. However, in some cases, clinicians have to consider combining a full ceramic crown with a metal post core. Therefore, this experiment was conducted to test the esthetical possibility of applying cast metal post core in a full ceramic crown restoration. The color of full ceramic crowns on gold and Nickel-Chrome post cores was compared with the color of the same crowns on tooth colored post cores. Different try-in pastes were used to imitate the influence of a composite cementation on the color of different restorative combinations. The majority of patients could not detect any color difference less than DeltaE 1.8 between the two ceramic samples. So, DeltaE 1.8 was taken as the objective evaluative criterion for the evaluation of color matching and patients' satisfaction. When the Empress 2 crown was combined with the gold alloy post core, the color of the resulting material was similar to that of a glass fiber reinforced resin post core (DeltaE = 0.3). The gold alloy post core and the try-in paste did not show a perceptible color change in the full ceramic crowns, which indicated that the color of the crowns might not be susceptible to change between lab and clinic as well as during the process of composite cementation. Without an opaque covering the Ni-Cr post core would cause an unacceptable color effect on the crown (DeltaE = 2.0), but with opaque covering, the color effect became more clinically satisfactory (DeltaE = 1.8). It may be possible to apply a gold alloy post core in the Empress 2 full ceramic crown restoration when necessary. If a non-extractible Ni-Cr post core exists in the root canal, it might be possible to restore the tooth with an Empress 2 crown after covering the labial surface of the core with one layer of opaque resin cement.

  12. Swimming black-crowned night-herons (Nycticorax nycticorax) Kleptoparasitize American coots (Fulica americana)

    DEFF Research Database (Denmark)

    Graves, Gary R.

    2015-01-01

    I observed black-crowned night-herons (Nycticorax nycticorax) swimming and kleptoparasitizing American coots (Fulica americana) at an artificial lake in Pinal County, Arizona. This appears to be the first record of interspecific kleptoparasitism by a swimming ardeid.......I observed black-crowned night-herons (Nycticorax nycticorax) swimming and kleptoparasitizing American coots (Fulica americana) at an artificial lake in Pinal County, Arizona. This appears to be the first record of interspecific kleptoparasitism by a swimming ardeid....

  13. RICHMOND CROWN - FOR RESTORATION OF BADLY MUTILATED POSTERIOR TEETH : A CASE REPORT

    OpenAIRE

    Yadav; Swetha

    2015-01-01

    Restoration of badly broken endodontically treated teeth is a common problem in restorative dentistry. Such teeth often require additional support from the root canal by means of a post and core restoration. In cases where tooth structure is significantly lost full coverage restorations for posterior teeth are necessary to achieve proper tooth form and function. Badly broken teeth with minimal or no crown structure require added retention and support. The Richmond crown can be a good treatmen...

  14. Distribution and prevalence of crown rot pathogens affecting wheat crops in southern Chile

    Directory of Open Access Journals (Sweden)

    Ernesto Moya-Elizondo

    2015-03-01

    Full Text Available Crown rot pathogens are associated with higher losses for wheat crop farmers, but information about the distribution and prevalence of these pathogens in Chile is inadequate. Distribution and prevalence of wheat (Triticum aestivum L. crown rot pathogens were examined in a survey of 48 commercial fields from December 2011 to February 2012 in southern Chile. These fields were located between Collipulli (37°56'00" S; 72°26'39" W and Purranque (40°50'30" S; 73°22'03" W. Severity of crown rot disease was determined through visual assessment of the first internode of 20 tillers obtained from each field. Incidence of crown rot pathogens per field was determined by plating the 20 tillers on Petri plates with 20% potato dextrose agar amended with lactic acid (aPDA medium. Resulting fungal colonies from monoxenic culture were identified by morphological or molecular-assisted identification. Severity of crown rot varied between 11.3% and 80% for individual fields. Culture plate analysis showed 72.2% of stems were infected with some fungus. Fusarium avenaceum, F. graminearum, and F. culmorum, pathogens associated with Fusarium crown rot disease were isolated from 13.5% of tillers. Gaeumannomyces graminis, causal agent of take-all disease in cereals, was isolated from 11.1% of culms. Phaeosphaeria sp., an endophyte and possibly a non-pathogenic fungus, was isolated from 13.9% of tillers. Pathogenic fungi such as Rhizoctonia spp. and Microdochium nivale, other saprophyte, and several unidentified non-sporulating fungi were isolated at frequencies lower than 3% of the total. Fusarium crown rot and take-all were the most prevalent and distributed crown rot diseases present in wheat crops in southern Chile.

  15. Crown-Stump Diameter Model for Parkia biglobosa Benth. Species in Makurdi, Benue State, Nigeria

    Directory of Open Access Journals (Sweden)

    O. Chukwu

    2017-07-01

    Full Text Available The crown of tree is the centre of physiological activity which gives an indication of the potential photosynthetic capacity on a tree. Though, its measurement remains a challenge in forest inventory task. The ability to predict crown diameter from stump diameter provides an effective technique of obtaining its estimate. This helps in detecting the excessive tree felling than actual requirements and wildlife suitability.The main objective of this study was to develop and test crown diameter prediction models for silvicultural management of naturally grown Parkia biglobosa within the University of Agriculture, Makurdi. Nine 100 m x 100 m temporary sample plots were established using simple random sampling method. Crown diameter and stump diameter were measured in all living P. biglobosa trees with stump diameter ≥10.0 cm. Least square method was used to convert the counted stumps into harvested crown dimension. Three linear and three non-linear models using stump diameter as the exploratory variable were developed and evaluated using the adjusted coefficient of determination (Adj.R2, standard error of estimate (SEE, prediction error sum of squares (PRESS and Akaike information criterion (AIC. The crown-stump diameter relationship was best described by the double logarithmic function with .The result showed that Crown diameter estimation was feasible even when the only information available is stump diameter.The resulting equation was tested for validation with independent data obtained from additional plots and was found to be desirable for estimating the crown diameter for Parkia biglobosa in Makurdi, Benue State, Nigeria.

  16. Influence of coping design on the cervical color of ceramic crowns.

    Science.gov (United States)

    Paniz, Gianluca; Kang, Ki-Ho; Kim, Yongjeong; Kumagai, Naota; Hirayama, Hiroshi

    2013-12-01

    The replication of natural teeth, especially with single-tooth restorations, represents a challenge. Similar to metal ceramic crowns, different designs of zirconia substructures have been suggested to improve the esthetic results of zirconia ceramic crowns. The purpose of the study was to analyze the color of the cervical portion of single zirconia ceramic crowns fabricated with different zirconia coping designs. The color, measured on the CIELAB color scale, of 3 different groups of restorations (n=10) fabricated with zirconia coping (Lava) and feldspathic porcelain (Noritake Super Porcelain) was analyzed with a spectrophotometer. Conventional zirconia crowns with zirconia facial margins were compared with ceramic crowns with porcelain facial margins and either a horizontal reduction of the zirconia coping (1.0 mm reduction) or an additional vertical reduction (1.0 mm additional reduction). The 3 groups, each with a different coping extension, were examined with a 1-way ANOVA and the Fisher exact test, and the differences of the groups were evaluated by applying ΔE thresholds (α=.05). The mean color difference among all the groups was not clinically significant (ΔEcolor differences were present between the 2 porcelain butt margin groups of crowns (ΔE=1.06, between group H and V). Increased differences were present between the zirconia margin group and the porcelain butt margin group (ΔE=2.54 between group C and H; ΔE=2.41 between group C and V). Lab* values were examined in all the groups of crowns to determine the clinical implications. Within the limitation of the study, no significant differences were present among the tested groups of crowns. Nevertheless, although some differences were present between the zirconia margin group and the porcelain butt margin group, reduced differences were present between the 2 different cutback designs. Copyright © 2013 Editorial Council for the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights

  17. Highly selective and sensitive macrocycle-based dinuclear foldamer for fluorometric and colorimetric sensing of citrate in water.

    Science.gov (United States)

    Rhaman, Md Mhahabubur; Hasan, Mohammad H; Alamgir, Azmain; Xu, Lihua; Powell, Douglas R; Wong, Bryan M; Tandon, Ritesh; Hossain, Md Alamgir

    2018-01-10

    The selective detection of citrate anions is essential for various biological functions in living systems. A quantitative assessment of citrate is required for the diagnosis of various diseases in the human body; however, it is extremely challenging to develop efficient fluorescence and color-detecting molecular probes for sensing citrate in water. Herein, we report a macrocycle-based dinuclear foldamer (1) assembled with eosin Y (EY) that has been studied for anion binding by fluorescence and colorimetric techniques in water at neutral pH. Results from the fluorescence titrations reveal that the 1·EY ensemble strongly binds citrate anions, showing remarkable selectivity over a wide range of inorganic and carboxylate anions. The addition of citrate anions to the 1·EY adduct led to a large fluorescence enhancement, displaying a detectable color change under both visible and UV light in water up to 2 μmol. The biocompatibility of 1·EY as an intracellular carrier in a biological system was evaluated on primary human foreskin fibroblast (HF) cells, showing an excellent cell viability. The strong binding properties of the ensemble allow it to be used as a highly sensitive, detective probe for biologically relevant citrate anions in various applications.

  18. Implementation of anion-receptor macrocycles in supramolecular tandem assays for enzymes involving nucleotides as substrates, products, and cofactors.

    Science.gov (United States)

    Florea, Mara; Nau, Werner M

    2010-03-07

    A supramolecular tandem assay for direct continuous monitoring of nucleotide triphosphate-dependent enzymes such as potato apyrase is described. The underlying principle of the assay relies on the use of anion-receptor macrocycles in combination with fluorescent dyes as reporter pairs. A combinatorial approach was used to identify two complementary reporter pairs, i.e. an amino-gamma-cyclodextrin with 2-anilinonaphtalene-6-sulfonate (ANS) as dye (fluorescence enhancement factor of 17 upon complexation) and a polycationic cyclophane with 8-hydroxy-1,3,6-pyrene trisulfonate (HPTS) as dye (fluorescence decrease by a factor of more than 2000), which allow the kinetic monitoring of potato apyrase activity at different ATP concentration ranges (microM and mM) with different types of photophysical responses (switch-ON and switch-OFF). Competitive fluorescence titrations revealed a differential binding of ATP (strongest competitor) versus ADP and AMP, which constitutes the prerequisite for monitoring enzymatic conversions (dephosphorylation or phosphorylation) involving nucleotides. The assay was tested for different enzyme and substrate concentrations and exploited for the screening of activating additives, namely divalent transition metal ions (Ni(2+), Mg(2+), Mn(2+), and Ca(2+)). The transferability of the assay could be demonstrated by monitoring the dephosphorylation of other nucleotide triphosphates (GTP, TTP, and CTP).

  19. Corrosion mitigation of J55 steel in 3.5% NaCl solution by a macrocyclic inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Ambrish [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Southwest Petroleum University), Chengdu, Sichuan 610500 (China); Department of Chemistry, LFTS, Lovely Professional University, Phagwara, Punjab 144402 (India); Lin, Yuanhua, E-mail: yhlin28@163.com [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Southwest Petroleum University), Chengdu, Sichuan 610500 (China); Obot, I.B. [Centre of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Ebenso, Eno E. [Department of Chemistry, School of Mathematical & Physical Sciences, North-West University (Mafikeng Campus), Private Bag X2046, Mmabatho 2735 (South Africa); Material Science Innovation & Modelling (MaSIM) Focus Area, Faculty of Agriculture, Science and Technology, North-West University (Mafikeng Campus), Private Bag X2046, Mmabatho 2735 (South Africa); Ansari, K.R.; Quraishi, M.A. [Department of Applied Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005, Uttar Pradesh (India)

    2015-11-30

    Graphical abstract: SECM studies revealed decrease of steady current in the presence of inhibitor while it increased for 3.5% NaCl solution that acted as the conductor. - Highlights: • J55 steel protection in 3.5% NaCl solution saturated with CO{sub 2} by HPT. • Potentiodynamic polarization curves reveal that the actions of HPT are mixed type. • The adsorption of HPT obeys the Langmuir adsorption isotherm. • Scanning electrochemical microscopy is used to discuss the insulated and conductive surface. - Abstract: 1,2,4,7,9,10-Hexaazacyclo-pentadeca-10,15-dien-3,5,6,8-tetraone (HPT) a macrocyclic compound has been studied using electrochemical methods and scanning electrochemical microscopy (SECM) techniques. The R{sub ct} values increased and C{sub dl} values decreased with the increase in concentration of the inhibitor. The corrosion inhibition of J55 steel in 3.5 wt.% NaCl solution saturated with CO{sub 2} by polarization studies revealed that HPT acted as a mixed type inhibitor. The adsorption of HPT on the J55 steel surface obeyed the Langmuir adsorption isotherm. The thermodynamic parameters (K{sub ads}, ΔG°{sub ads}) were also computed and discussed.

  20. Corrosion mitigation of J55 steel in 3.5% NaCl solution by a macrocyclic inhibitor

    International Nuclear Information System (INIS)

    Singh, Ambrish; Lin, Yuanhua; Obot, I.B.; Ebenso, Eno E.; Ansari, K.R.; Quraishi, M.A.

    2015-01-01

    Graphical abstract: SECM studies revealed decrease of steady current in the presence of inhibitor while it increased for 3.5% NaCl solution that acted as the conductor. - Highlights: • J55 steel protection in 3.5% NaCl solution saturated with CO 2 by HPT. • Potentiodynamic polarization curves reveal that the actions of HPT are mixed type. • The adsorption of HPT obeys the Langmuir adsorption isotherm. • Scanning electrochemical microscopy is used to discuss the insulated and conductive surface. - Abstract: 1,2,4,7,9,10-Hexaazacyclo-pentadeca-10,15-dien-3,5,6,8-tetraone (HPT) a macrocyclic compound has been studied using electrochemical methods and scanning electrochemical microscopy (SECM) techniques. The R ct values increased and C dl values decreased with the increase in concentration of the inhibitor. The corrosion inhibition of J55 steel in 3.5 wt.% NaCl solution saturated with CO 2 by polarization studies revealed that HPT acted as a mixed type inhibitor. The adsorption of HPT on the J55 steel surface obeyed the Langmuir adsorption isotherm. The thermodynamic parameters (K ads , ΔG° ads ) were also computed and discussed.