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Sample records for thiaaza crown macrocycles

  1. Synthesis and Characterisation of Macrocyclic Diamino Chiral Crown Ethers

    Directory of Open Access Journals (Sweden)

    Janet L. Scott

    2004-05-01

    Full Text Available A benign and efficient synthesis of chiral macrocyclic ‘aza-crown’ ethers of varying ring size is reported. The synthesis involves a Schiff base condensation of ether linked dialdehydes of varying chain length and (1R,2R-(–-1,2-diaminocyclohexane under mild conditions to yield the macrocycles, which are subsequently reduced to yield the diamino analogues.

  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. 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.

  4. Influence of Macrocyclic Ring Size on the Corrosion Inhibition Efficiency of Dibenzo Crown Ether: A Density Functional Study

    Directory of Open Access Journals (Sweden)

    Saprizal Hadisaputra

    2017-11-01

    Full Text Available The effect of macrocycle ring size on the corrosion inhibition efficiency of dibenzo-12-crown-4 (DB12C4, dibenzo-15-crown-5 (DB15C5, dibenzo-18-crown-6 (DB18C6, dibenzo-21-crown-7 (DB21C7 and dibenzo-24-crown-8 (DB24C8 have been elucidated by mean of density functional calculation at B3LYP/6-31G(d level of theory in the gas and aqueous environment. The quantum chemical parameters including the frontier orbital energies (EHOMO, ELUMO, ionization potential (I, electron affinity (A, the absolute electronegativity (χ, hardness (η, softness (σ, and the fraction of electron transferred (ΔN are positively correlated to the corrosion inhibition efficiency (IE% of the studied crown ethers. The calculation results indicate that DB24C8 exhibits the highest corrosion inhibition efficiency, whereas DB12C4 exhibits the lowest corrosion inhibition efficiency. The results of this study will contribute to design crown ethers potential as corrosion inhibitors.

  5. Through-space electronic communication of zinc phthalocyanine with substituted [60]Fullerene bearing O2Nxaza-crown macrocyclic ligands

    Science.gov (United States)

    Ghanbari, Bahram; Shahhoseini, Leila; Mahlooji, Niloofar; Gholamnezhad, Parisa; Taheri Rizi, Zahra

    2017-01-01

    Two new macrocyclic ligands containing 17- and 19-membered O2N3-donor aza-crowns anchored to [60]Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, UV-vis, IR spectroscopies, as well as powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. TGA measurements revealed that upon linking each of these macrocycle rings to [60]Fullerene, the decomposition point measured for [60]Fullerene moiety was increased, indicating on the promoted stability of [60]Fullerene backbone during binding to these macrocyclic ligands. Moreover, the ground state non-covalent interactions of [60]Fullerene derivatives of O2Nx (x = 2, and 3) aza-crown macrocyclic ligands namely, L1-L4 with zinc phthalocyanine (ZnPc) were also investigated by UV-vis absorption, steady state and time resolved fluorescence spectrophotometry in N-methyl-2-pyrrolidone (NMP). The calculation of Stern-Volmer constants (KSV) indicated on existence of an efficient quenching mechanism comprising of the excited singlet state of ZnPc in the presence of L1-L4. The observation of an appropriate correlation between decrease in fluorescence intensity and lifetime parameters led us to propose the occurrence of a static mechanism for the fluorescence quenching of ZnPc in the presence of L1-L3. The binding constants (KBH) of L1-L4/ZnPc were also determined applying the fluorescence quenching experiments. Meanwhile, the incompatibility of both KSV and KBH values found for L4 was also described in terms of structural features using DFT calculations using the B3LYP functional and 6-31G* basis set.

  6. BINOL Macrocycle Derivatives: Synthesis of New Dinaphthyl Sulfide Aza Oxa Thia Crowns (Lariats

    Directory of Open Access Journals (Sweden)

    Abbas Shockravi

    2013-01-01

    Full Text Available In this research work, dinaphthyl sulfide diester was prepared from the reaction of 1,1′-thiobis (2-hydroxy naphthalene and methylchloroacetate. Its aza-macrocyclic derivative was synthesized from the reaction of dinaphthyl sulfide diester and diethylenetriamine. Lariats were prepared from the reaction of chloroamides (four derivatives and initial macrocycle. Chloroamides were synthesized from the reaction of amines (aniline, benzylamine, 8-amino quinoline and 4-amino azobenzene and chloroacetyl chloride. All the materials were identified by IR, 1H NMR, 13C NMR, and mass spectroscopies, and elemental analysis.

  7. Calix[4]arene-(2,3-naphthylene-crown-6,crown-6) as an extraordinarily efficient macrocyclic receptor for the univalent thallium cation

    Science.gov (United States)

    Makrlík, Emanuel; Böhm, Stanislav; Kvíčalová, Magdalena; Vaňura, Petr; Asfari, Zouhair

    2015-11-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Tl+ (aq) + 1.Cs+ (nb) ? 1.Tl+ (nb) + Cs+ (aq) taking place in the two-phase water-nitrobenzene system (1 = calix[4]arene-(2,3-naphthylene-crown-6,crown-6); aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex(Tl+,1.Cs+) = 0.3 ± 0.1. Further, the extremely high stability constant of the 1.Tl+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb(1.Tl+) = 10.0 ± 0.2. Finally, applying quantum mechanical calculations, the most probable structure of the cationic complex species 1.Tl+ was derived. In the resulting complex, the 'central' cation Tl+ is bound by eight strong bonds to six oxygen atoms of the crown-6 moiety and to two carbons from the respective two benzene rings of the parent ligand 1 via cation-π interaction. The interaction energy, E(int), of the considered 1.Tl+ complex was found to be -305.7 kJ/mol, also confirming the formation of this cationic species.

  8. Crowns and Crypts

    Indian Academy of Sciences (India)

    The product was isolated to be dibenzo-. 18-Crown-6. Many other crowns were ... fashion with their lone pairs pointing inward towards the metal atom. The bonding M-O is largely ... Macrocycles, though extremely effective as polydentate ligands, are not essential for the production of stable alkali complexes; additional ...

  9. Water's role in reshaping a macrocycle's binding pocket: infrared and ultraviolet spectroscopy of benzo-15-crown-5-(H(2)O)(n) and 4'-aminobenzo-15-crown-5-(H(2)O)(n), n = 1, 2.

    Science.gov (United States)

    Shubert, V Alvin; Müller, Christian W; Zwier, Timothy S

    2009-07-16

    Laser-induced fluorescence (LIF), resonant two-photon ionization (R2PI), ultraviolet hole-burning (UVHB), resonant ion-dip infrared (RIDIR), and infrared-infrared ultraviolet hole-burning (IR-IR-UV) spectroscopies were carried out on benzo-15-crown-5 ether-(H(2)O)(n) (B15C-(H(2)O)(n)) and 4'-amino-benzo-15-crown-5 ether-(H(2)O)(n) (ABC-(H(2)O)(n)) clusters with n = 1,2 formed in a supersonic expansion. Two isomers of B15C-(H(2)O)(1) with S(0)-S(1) origins at 35,628 and 35,685 cm(-1) (B15C-(H(2)O)(1)(A) and B15C-(H(2)O)(1)(B), respectively) were identified and, on the basis of the combined evidence from the single-isomer UV and IR spectra, assigned to structures in which the H(2)O molecule donates both its OH groups to H-bonds to the crown oxygens. Both isomers share the same open, chairlike C(s) symmetry structure for the crown ether that exposes the crown oxygen lone pairs to binding to H(2)O on the interior of the crown. This crown conformation is not among those represented in the observed conformers in the absence of the H(2)O molecule, indicating that even a single water molecule is capable of reshaping the crown binding pocket in binding to it. In B15C-(H(2)O)(1)(A), the water molecule takes up a position parallel to the crown plane of symmetry, using one OH group to bind to the two benzo oxygens, while the other OH binds to a single crown oxygen on the opposite side of the crown. The H(2)O molecule in B15C-(H(2)O)(1)(B) binds to the other two crown oxygens, in an orientation perpendicular to the crown's symmetry plane. B15C-(H(2)O)(2) also has two isomers. The first, B15C-(H(2)O)(2)(A) with S(0)-S(1) origin at 35,813 cm(-1), is assigned to a structure in which the two water molecules take up the two positions occupied by individual water molecules in B15C-(H(2)O)(1) A and B. The second isomer, with S(0)-S(1) origin at 35,665 cm(-1), has an OH stretch RIDIR spectrum that reflects a water-water H-bond, with the second water molecule binding to the crown

  10. 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:

  11. 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".

  12. 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...... 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....../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...

  13. Synthesis of Crown Ethers Containing a Rubicene Moiety

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    Mario Smet

    2000-03-01

    Full Text Available A symmetrically disubstituted derivative of the highly fluorescing and photostable rubicene was incorporated in a macrocycle using high dilution conditions and a hydroxyrubicene was functionalized with a modified aminobenzo-15-crown-5.

  14. Luminescent macrocyclic lanthanide complexes

    Science.gov (United States)

    Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide

    2014-05-20

    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  15. Dental crowns

    Science.gov (United States)

    ... than metal crowns Match the color of other teeth May be a good choice if you have a metal allergy Porcelain fused to metal crowns: Are made from porcelain covering a metal crown Metal makes the crown stronger Porcelain part is more prone to fracture than crowns made of all porcelain After the ...

  16. SYNTHESIS, COMPLEXATION BEHAVIOR AND REACTIONS OF THIA-CROWN ETHERS INCORPORATING PROPAN-2-ONE UNITS

    NARCIS (Netherlands)

    KELLOGG, RM; VANBOLHUIS, F

    1991-01-01

    Thia-crown ethers containing ketone functionality derived from 1,3-dichloroacetone have been prepared in 70-80% yields; the crystal structures of one free macrocycle and two Ag1 complexes have been determined.

  17. 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.

  18. 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

  19. 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

  20. Activity relationships for aromatic crown ethers

    CERN Document Server

    Wilson, M J

    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...

  1. Recent Advances in Macrocyclic Fluorescent Probes for Ion Sensing

    Directory of Open Access Journals (Sweden)

    Joseph K.-H. Wong

    2017-01-01

    Full Text Available Small-molecule fluorescent probes play a myriad of important roles in chemical sensing. Many such systems incorporating a receptor component designed to recognise and bind a specific analyte, and a reporter or transducer component which signals the binding event with a change in fluorescence output have been developed. Fluorescent probes use a variety of mechanisms to transmit the binding event to the reporter unit, including photoinduced electron transfer (PET, charge transfer (CT, Förster resonance energy transfer (FRET, excimer formation, and aggregation induced emission (AIE or aggregation caused quenching (ACQ. These systems respond to a wide array of potential analytes including protons, metal cations, anions, carbohydrates, and other biomolecules. This review surveys important new fluorescence-based probes for these and other analytes that have been reported over the past five years, focusing on the most widely exploited macrocyclic recognition components, those based on cyclam, calixarenes, cyclodextrins and crown ethers; other macrocyclic and non-macrocyclic receptors are also discussed.

  2. Macrocyclic ligands for uranium complexation

    Energy Technology Data Exchange (ETDEWEB)

    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{sup 0} chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs.

  3. 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

  4. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.

    1990-04-01

    Macrocycles with cavity diameters in the region 4.5-5.2 Angstrom, based on computer modeling studies, have been prepared by high dilution cyclocondensation of 2-aminopyridyl substituted biurets and thiobiurets with appropriately substituted, reactive intermediates such as chlorocarbonyl isocyanate and malonyl dichloride. Detailed high field 1 H NMR studies have been used to identify all protons in these macrocycles for structural verification and in confromation studies, and by-products obtained in their synthesis as well as in complexation studies have been characterized and identified using these NMR techniques, as well as single crystal X-ray studies. 5 refs

  5. Macrocyclic cyclodiphosphazane : synthesis of chalcogen ...

    Indian Academy of Sciences (India)

    VITTHALRAO S KASHID

    2017-09-06

    Sep 6, 2017 ... 6. Calera S G and Wright D S 2010 Macrocyclic phosphaz- ane ligands Dalton Trans. 39 5055. 7. Gonzalez-Calera S, Eisler D J, Morey J V, McPartlin M, .... Silaghi-Dumitrescu I, Lara-Ochoa F and Haiduc I 1998. Edge or Verte Inversion at Phosphorus in the cis-trans. Isomerization of Diazadiphosphetidines ...

  6. 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

  7. Triaquachlorido(18-crown-6barium chloride

    Directory of Open Access Journals (Sweden)

    Min-Min Zhao

    2012-03-01

    Full Text Available In the title compound, [BaCl(C12H24O6(H2O3]Cl, the BaII atom, the coordinating and free Cl− anions, one coordinating water molecule and two O atoms of an 18-crown-6 molecule lie on a mirror plane. The environment of the ten-coordinate Ba2+ ion is defined by one Cl atom, three water molecules and six O atoms from the macrocyclic ether. The macrocycle adopts a conformation with an approximate D3d symmetry. In the crystal, O—H...Cl hydrogen bonds link the complex cations and Cl− anions into a two-dimensional network parallel to (010. An intramolecular O—H...Cl hydrogen bond is also present.

  8. Macrocyclic cyclodiphosphazane : synthesis of chalcogen ...

    Indian Academy of Sciences (India)

    VITTHALRAO S KASHID

    2017-09-06

    Sep 6, 2017 ... Abstract. The synthesis of a Schiff base-appended macrocycle [{P(μ-tBuN)}2(O − m − C6H4CHNCH2)2]2. (1) containing cyclodiphosphazane moieties is described. Reactions of 1 with H2O2 and elemental selenium yielded derivatives tetrakis(oxide) [{P(O)(μ-tBuN)}2(O − m − C6H4CHNCH2)2]2 (2) and.

  9. 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

  10. Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles

    DEFF Research Database (Denmark)

    Jana, Atanu; Ishida, Masatoshi; Park, Jung Su

    2017-01-01

    , organic field-effect transistors, and optical sensors. Modified TTF structures thus constitute promising candidates for the development of so-called “functional materials” that could see use in modern technological applications. The versatility of the TTF unit and the pioneering synthetic strategies...... that have been developed over the past few decades provide opportunities to tune the architecture and function for specific purposes. This review covers the “state of the art” associated with TTF-annulated oligopyrrolic macrocyclic compounds. Points of emphasis include synthesis, properties, and potential...

  11. Crown ethers as size-selective synergists in solvent extraction systems: a new selectivity parameter

    International Nuclear Information System (INIS)

    Kinard, W.F.; McDowell, W.J.

    1981-01-01

    Mixtures of macrocyclic polyethers (crown ethers) and organic-phase-soluble liquid cation exchangers have been found to produce a synergistic effect in the extraction of metal ions. The synergistic effect is size selective; that is, it tends to be greatest for those ions that best fit the crown ether cavity. The mixtures of a liquid cation exchanger and a crown ether also allow metal ion extraction from common mineral-acid anion systems (NO 3 - , Cl - , SO 4 2- ) that would be impossible with the crown ether alone, because of the difficulty of solubilizing those anions in nonpolar solvents. This cooperation makes the use of crown ethers as size-selective coordinators available for process applications. Size selectivity of compounds such as crown ethers may thus become a useful new parameter in designing selective solvent extraction systems. Results are reported for alkali (including Cs) and alkaline earth (including Sr) extraction by HDEHP mixed with various crown ethers. (author)

  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. Radical photocyclization route for macrocyclic lactone ring expansion and conversion to macrocyclic lactams and ketones.

    Science.gov (United States)

    Nishikawa, Keisuke; Yoshimi, Yasuharu; Maeda, Kousuke; Morita, Toshio; Takahashi, Ichiro; Itou, Tatsuya; Inagaki, Sho; Hatanaka, Minoru

    2013-01-18

    A new method for the synthesis of macrocyclic lactones, lactams, and ketones, which utilizes photoinduced intramolecular radical cyclization reactions of substrates containing tethered carboxylic acids and α,β-unsaturated carbonyl moieties, has been uncovered. Photocyclization of the carboxylic acids tethered acrylate ester, which were prepared starting from the macrocyclic lactones, gave the two-carbon elongated macrocyclic lactones via decarboxylation. Similar photoreactions of carboxylic acid tethered acryl amide or α,β-unsaturated ketone moieties, which were also prepared starting from the macrocyclic lactones, produced macrocyclic lactams or ketones, respectively. The simple approach can be readily applied to the preparation of a variety of macrocyclic lactones, lactams, and ketones with tunable ring sizes.

  14. 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

  15. Experimental and theoretical study on complexation of the ammonium cation with dibenzo-30-crown-10

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Toman, Petr; Vaňura, P.

    2012-01-01

    Roč. 143, č. 5 (2012), s. 711-715 ISSN 0026-9247 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505 Keywords : crown ethers * macrocycles * complexation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.629, year: 2012

  16. Theoretical study on the complexation of the cesium cation with dibenzo-18-crown-6

    Czech Academy of Sciences Publication Activity Database

    Toman, Petr; Makrlík, E.; Vaňura, P.

    2011-01-01

    Roč. 142, č. 6 (2011), s. 569-571 ISSN 0026-9247 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505 Keywords : crown ethers * macrocycles * complexation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.532, year: 2011

  17. 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...

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. A combined experimental and theoretical study on the complexation of the ammonium ion with benzo-18-crown-6

    Czech Academy of Sciences Publication Activity Database

    Toman, Petr; Makrlík, E.; Vaňura, P.

    2010-01-01

    Roč. 141, č. 3 (2010), s. 301-304 ISSN 0026-9247 Institutional research plan: CEZ:AV0Z40500505 Keywords : crown ethers * macrocycles * Ab initio calculations Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.356, year: 2010

  3. A combined extraction and DFT study on the complexation of the silver cation with dibenzo-18-crown-6

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Toman, Petr; Vaňura, P.

    2011-01-01

    Roč. 142, č. 2 (2011), s. 137-140 ISSN 0026-9247 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505 Keywords : crown ethers * macrocycles * complexation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.532, year: 2011

  4. Pharmacologically significant tetraaza macrocyclic metal complexes ...

    Indian Academy of Sciences (India)

    MOHAMMAD SHAKIR

    2017-11-22

    Nov 22, 2017 ... along with medical sector (up to 60% of the total human infections are provoked by biofilms).24–26 The Candida biofilms formation has an important ..... 784.01 respectively, correspond to the nitrogen isotope. The mass spectra of Schiff base macrocyclic complexes of Co(II), (a) Ni, (b) Cu(II), (c) and Zn(II), ...

  5. 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...

  6. THE INFLUENCE OF ANION NATURE OF ALKALINE METAL SALT ON SPECTRAL-LUMINESCENT PROPERTIES OF F-S-HETERONUCLEAR COMPLEXES ON THE BASE OF CROWN-PORPHYRINS

    Directory of Open Access Journals (Sweden)

    N. V. Rusakova

    2016-04-01

    Full Text Available The heteronuclear complexes on the base of meso-tetra-crown-ether substituted porphyrins of «sandwich»-type which two ytterbium ions coordinated with porphyrin macrocycles, and four cations of alkaline metals (Na, K, Cs situated between the cavities of benzo-12-crown-4-, benzo-15-crown-5- and benzo-18-crown-6-ethers, respectively, were obtained. The influence of anion nature of salts (bromide, nitrate, thiocyanate on 4f-luminescence of Yb8+ ions in these complexes were analyzed.

  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. 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

  9. 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.

  10. The unusual macrocycle forming thioesterase of mycolactone.

    Science.gov (United States)

    Meier, Jordan L; Barrows-Yano, Tiffany; Foley, Timothy L; Wike, Candice L; Burkart, Michael D

    2008-06-01

    Mycolactone is a polyketide natural product secreted by Mycobacterium ulcerans, the organism responsible for the tropical skin disease Buruli ulcer. The finding that this small molecule virulence factor is sufficient to reconstitute the necrotic pathology associated with Buruli ulcer suggests that a better understanding of mycolactone biosynthesis, particularly the processes which are distinct from those in human metabolism, may provide a unique avenue for the development of selective therapeutics. In the present study we have cloned, expressed, and biochemically characterized the putative macrocycle forming thioesterase for mycolactone, MLSA2 TE. We have evaluated the enzyme both as the truncated thioesterase domain and as a carrier protein-linked didomain construct. The results of these analyses distinguish MLSA2 TE from traditional fatty acid and polyketide synthase TE-domains in terms of its sequence, kinetic parameters, and susceptibility to traditional active-site directed inhibitors. These findings suggest that MLSA2 TE utilizes a unique biochemical mechanism for macrocycle formation.

  11. 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

  12. 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.)

  13. 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.)

  14. Liquid-Liquid Extraction of Transition Metal Cations by Glyoximes and Their Macrocyclic Glyoxime Ether Derivatives

    Directory of Open Access Journals (Sweden)

    Nazan Karapinar

    2013-01-01

    Full Text Available Liquid-liquid extraction of various alkalis (Li+, Na+, K+, and Cs+, transition metals (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+, and Pb2+ cations with phenylglyoxime (L1, p-tolylglyoxime (L2, N′-(4′-Benzo[15-crown-5]phenylaminoglyoxime (L3, and N′-(4′-Benzo[15-crown-5]-p-tolylaminoglyoxime (L4 from the aqueous phase into the organic phase was carried out. For comparison, the corresponding two glyoximes and their macrocyclic glyoxime ether derivatives were also examined. Crown ether groups having ligands (L3, L4 carry especially Na+ cation from aqueous phase to organic phase. The extraction equilibrium constants (Kex for complexes of ligands with Cu2+ and Hg2+ metal picrates between dichloromethane and water have been determined at 25°C. The values of the extraction constants (logKex were determined to be 12.27, 13.37, 12.94, and 12.39 for Cu2+ and 10.29, 10.62, 11.53, and 11.97 for Hg2+ with L1–L4, respectively.

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

    Indian Academy of Sciences (India)

    Introduction. The chemical behaviour of transition-metal complexes often depends on their redox properties. This is true to a large extent for the natural and synthetic complexes involving macrocyclic ligands such as Ni(II) hexaaza and pentaaza macrocyclic derivatives which are known to display properties and reactivity ...

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

    Indian Academy of Sciences (India)

    Almost all Ni(II) macrocyclic complexes investigated so far, display the typical macrocyclic inertness towards demetallation by strong acids 11. Most of the Ni(II) complexes have been isolated as perchlorate salts by the addition of concentrated perchloric acid to the reaction solution. These salts are water soluble and show ...

  17. Antibacterial and antioxidant properties of macrocyclic Schiff bases ...

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    Also in-vitro antioxidant activity of all compounds was determined by nitric acid free radical scavanging assay. Keywords: Macrocyclic Schiff Bases; Vanadium complexes; Antibacterial; Antioxidant activities. 1. INTRODUCTION. The macrocyclic ligands are highly significant in bioinorganic chemistry, catalysis, extraction of ...

  18. 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.

  19. 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.

  20. 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

  1. Guanidinium/ammonium competition and proton transfer in the interaction of the amino acid arginine with the tetracarboxylic 18-crown-6 ionophore.

    Science.gov (United States)

    Avilés-Moreno, Juan Ramón; Berden, Giel; Oomens, Jos; Martínez-Haya, Bruno

    2018-02-07

    The recognition of arginine plays a central role in modern proteomics and genomics. Arginine is unique among natural amino acids due to the high basicity of its guanidinium side chain, which sustains specific interactions and proton exchange biochemical processes. The search for suitable macrocyclic ionophores constitutes a promising route towards the development of arginine receptors. This study evaluates the conformational features involved in the binding of free arginine by the polyether macrocycle (18-crown-6)-tetracarboxylic acid. Infrared action vibrational spectroscopy and quantum-chemical computations are combined to characterize the complexes with net charges +1 and +2. The spectrum of the +1 complex can be explained in terms of a configuration predominantly stabilized by a robust bidentate coordination of guanidinium with a carboxylate group formed from the deprotonation of one side group of the crown ether. The released proton is transferred to the amino terminus of arginine, which then coordinates with the crown ether ring. In an alternative type of conformation, partly consistent with experiment, the amino terminus is neutral and the guanidinium group inserts into the crown ether cavity. In the +2 complexes, arginine is always doubly protonated and the most stable conformations are characterized by a tripodal coordination of the ammonium -NH 3 + group of arginine with the oxygen atoms of the macrocycle ring, while the interactions of the amino acid with the side carboxylic acid groups of the crown ether acquire a remarkable lesser role.

  2. 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...

  3. Direct and indirect single electron transfer (SET-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers

    Directory of Open Access Journals (Sweden)

    Dae Won Cho

    2014-02-01

    Full Text Available In this review, we describe direct and indirect photochemical approaches that have been developed for the preparation of phthalimide- and naphthalimide-based, lariat-type crown ethers. The direct route utilizes a strategy in which nitrogen-linked side chains containing polyethoxy-tethered phthalimides and naphthalimides, possessing terminal α-trialkylsilyl groups, are synthesized utilizing concise routes and UV-irradiation to form macrocyclic ring systems. In contrast, the indirect route developed for the synthesis of lariat-type crown ethers employs sequences in which SET-promoted macrocyclization reactions of α-trialkylsilyl-terminated, polyethoxy-tethered phthalimides and naphthalimides are followed by a side chain introduction through substitution reactions at the amidol centers in the macrocyclic ethers. The combined observations made in these investigations demonstrate the unique features of SET-promoted photocyclization reactions that make them well-suited for the use in the synthesis of functionalized crown ethers. In addition, while some limitations exist for the general use of SET-photochemical reactions in large-scale organic synthesis, important characteristics of the photoinduced macrocyclization reactions make them applicable to unique situations in which high temporal and spatial control is required.

  4. Supramolecular polymers constructed from macrocycle-based host-guest molecular recognition motifs.

    Science.gov (United States)

    Dong, Shengyi; Zheng, Bo; Wang, Feng; Huang, Feihe

    2014-07-15

    /physical properties, including stimuli responsiveness, self-healing, and environmental adaptation. It has been reported that macrocycle-based supramolecular polymers can respond to pH change, photoirradition, anions, cations, temperature, and solvent. Macrocycle-based supramolecular polymers have been prepared in solution, in gel, and in the solid state. Furthermore, the solvent has a very important influence on the formation of these supramolecular polymers. Crown ether- and pillararene-based supramolecular polymers have mainly formed in organic solvents, such as chloroform, acetone, and acetonitrile, while cyclodextrin- and cucurbituril-based supramolecular polymerizations have been usually observed in aqueous solutions. For calixarenes, both organic solvents and water have been used as suitable media for supramolecular polymerization. With the development of supramolecular chemistry and polymer science, various methods, such as nuclear magnetic resonance spectroscopy, X-ray techniques, electron microscopies, and theoretical calculation and computer simulation, have been applied for characterizing supramolecular polymers. The fabrication of macrocycle-based supramolecular polymers has become a currently hot research topic. In this Account, we summarize recent results in the investigation of supramolecular polymers constructed from macrocycle-based host-guest molecular recognition motifs. These supramolecular polymers are classified based on the different macrocycles used in them. Their monomer design, structure control, stimuli-responsiveness, and applications in various areas are discussed, and future research directions are proposed. It is expected that the development of supramolecular polymers will not only change the way we live and work but also exert significant influence on scientific research.

  5. Design and Synthesis of Novel Macrocyclic Mer Tyrosine Kinase Inhibitors.

    Science.gov (United States)

    Wang, Xiaodong; Liu, Jing; Zhang, Weihe; Stashko, Michael A; Nichols, James; Miley, Michael J; Norris-Drouin, Jacqueline; Chen, Zhilong; Machius, Mischa; DeRyckere, Deborah; Wood, Edgar; Graham, Douglas K; Earp, H Shelton; Kireev, Dmitri; Frye, Stephen V

    2016-12-08

    Mer tyrosine kinase (MerTK) is aberrantly elevated in various tumor cells and has a normal anti-inflammatory role in the innate immune system. Inhibition of MerTK may provide dual effects against these MerTK-expressing tumors through reducing cancer cell survival and redirecting the innate immune response. Recently, we have designed novel and potent macrocyclic pyrrolopyrimidines as MerTK inhibitors using a structure-based approach. The most active macrocycles had an EC 50 below 40 nM in a cell-based MerTK phosphor-protein ELISA assay. The X-ray structure of macrocyclic analogue 3 complexed with MerTK was also resolved and demonstrated macrocycles binding in the ATP binding pocket of the MerTK protein as anticipated. In addition, the lead compound 16 (UNC3133) had a 1.6 h half-life and 16% oral bioavailability in a mouse PK study.

  6. Crowns and Crypts

    Indian Academy of Sciences (India)

    biologically occurring natural compounds they are expected to provide insight into the biological phenomena occurring in living systems. For example, the mechanism of the sodium pump occurring across a cell membrane could be understood using the formation of the alkali metal-crown complex mecha- nism as a model.

  7. CHEMICALLY MODIFIED FIELD-EFFECT TRANSISTORS - POTENTIOMETRIC AG+ SELECTIVITY OF PVC MEMBRANES BASED ON MACROCYCLIC THIOETHERS

    NARCIS (Netherlands)

    BRZOZKA, Z; COBBEN, PLHM; REINHOUDT, DN; EDEMA, JJH; KELLOGG, RM

    1993-01-01

    A chemically modified field-effect transistor (CHEMFET) with satisfactory Ag+ selectivity is described. The potentiometric Ag+ selectivities of CHEMFETs with plasticized PVC membranes based on macrocyclic thioethers have been determined. All the macrocyclic thioethers tested showed silver response

  8. Crown lengthening procedures

    Directory of Open Access Journals (Sweden)

    AA. Khoshkhonejad

    1994-06-01

    Full Text Available Nowadays, due to recent developments and researches in dental science, it is possible to preserve and restore previously extracted cases such as teeth with extensive caries, fractured or less appropriate cases for crown coverage as well as teeth with external perforation caused by restorative pins. In order to restore the teeth with preservation of periodontium, we should know thoroughly physiological aspects of periodontium and protection of Biologic Width which is formed by epithelial and supracrestal connective tissue connections. Considering biologic width is one of the principal rules of teeth restoration, otherwise we may destruct periodontal tissues. Several factors are involved in placing a restoration and one of the most important ones is where the restoration margin is terminated. Many studies have been conducted on the possible effects of restoration margin on the gingiva and due to the results of these studies it was concluded that restoration margin should be finished supragingivally. However, when we have to end the restoration under Gingival Crest, First a healthy gingival sulcus is required. Also, we should not invade the biological width. Since a normal biologic with is reported 2 mm and sound tooth tissue should be placed at least 2 mm coronal to the epithelial tissue, the distance between sound tooth tissue and crown margin should be at least 4mm. Thus, performing crown lengthening is essential to increase the clinical crown length. Basically, two objectives are considered: 1 restorative 2 esthetic (gummy smile Surgical procedure includes gingivectomy and flap procedure. Orthodontic procedure involves orthodontic extrusion or force eruption technique which is controlled vertical movements of teeth into occlusion. Besides, this procedure can also used to extrude teeth defects from the gingival tissue. By crown lengthening, tooth extraction is not required and furthermore, adjacent teeth preparation for placing a fixed

  9. Macrocyclic Assembly: A Dive into the Pecking Order and Applied Aspects of Multitalented Metallomacrocycles

    Directory of Open Access Journals (Sweden)

    Ashu Chaudhary

    2014-01-01

    Full Text Available To aid in knowledge of macrocyclic complexes and biomedical scientists, we are presenting here a review article with compilation of work done so far along in relation to macrocyclic ligands and their metal complexes. The metal ion chemistry of macrocyclic ligands has now become a major subdivision of coordination chemistry. This overview focuses on developments in design, synthesis, and self-assembly of metal-based architectures and ligands related to macrocyclic chemistry.

  10. Discovery of Macrocyclic Pyrimidines as MerTK-Specific Inhibitors.

    Science.gov (United States)

    McIver, Andrew L; Zhang, Weihe; Liu, Qingyang; Jiang, Xinpeng; Stashko, Michael A; Nichols, James; Miley, Michael J; Norris-Drouin, Jacqueline; Machius, Mischa; DeRyckere, Deborah; Wood, Edgar; Graham, Douglas K; Earp, H Shelton; Kireev, Dmitri; Frye, Stephen V; Wang, Xiaodong

    2017-02-03

    Macrocycles have attracted significant attention in drug discovery recently. In fact, a few de novo designed macrocyclic kinase inhibitors are currently in clinical trials with good potency and selectivity for their intended target. In this study, we successfully engaged a structure-based drug design approach to discover macrocyclic pyrimidines as potent Mer tyrosine kinase (MerTK)-specific inhibitors. An enzyme-linked immunosorbent assay (ELISA) in 384-well format was employed to evaluate the inhibitory activity of macrocycles in a cell-based assay assessing tyrosine phosphorylation of MerTK. Through structure-activity relationship (SAR) studies, analogue 11 [UNC2541; (S)-7-amino-N-(4-fluorobenzyl)-8-oxo-2,9,16-triaza-1(2,4)-pyrimidinacyclohexadecaphane-1-carboxamide] was identified as a potent and MerTK-specific inhibitor that exhibits sub-micromolar inhibitory activity in the cell-based ELISA. In addition, an X-ray structure of MerTK protein in complex with 11 was resolved to show that these macrocycles bind in the MerTK ATP pocket. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Columnar Liquid Crystals from a Giant Macrocycle Mesogen.

    Science.gov (United States)

    Kawano, Shin-Ichiro; Kato, Masahiro; Soumiya, Shinya; Nakaya, Masato; Onoe, Jun; Tanaka, Kentaro

    2018-01-02

    Columnar liquid crystals composed of a giant macrocyclic mesogen were prepared. The giant macrocyclic mesogen has a square hollow with a 2.5 nm diagonal, which was bounded by diindolo[3,2-b:2',3'-h]carbazole (diindolocarbazole) moieties as the edges and bis(salicylidene)-o-phenylenediamine (salphen) moieties as the corners. The shape and size of the macrocycle were directly observed by scanning tunneling microscopy (STM). Each side of the bright square in the STM image corresponds to a diindolocarbazole moiety, and the length of the sides was consistent with the result of the single crystal analysis of diindolocarbazole. Finally, we successfully obtained a giant macrocycle with long and branched side chains, which exhibited a rectangular columnar LC phase over a wide temperature range. To the best of our knowledge, it contained the largest discrete inner space of any thermotropic columnar liquid crystal composed of macrocyclic mesogens. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Control of olefin geometry in macrocyclic ring-closing metathesis using a removable silyl group.

    Science.gov (United States)

    Wang, Yikai; Jimenez, Miguel; Hansen, Anders S; Raiber, Eun-Ang; Schreiber, Stuart L; Young, Damian W

    2011-06-22

    Introducing a silyl group at one of the internal olefin positions in diolefinic substrates results in E-selective olefin formation in macrocyclic ring-forming metathesis. The application of this method to a range of macrocyclic (E)-alkenylsiloxanes is described. Protodesilylation of alkenylsiloxane products yields novel Z-configured macrocycles.

  13. 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....

  14. Cyclic and Macrocyclic Organic Compounds - a Personal Review in Honor of Professor Leopold Ružička

    Directory of Open Access Journals (Sweden)

    Höcker¸, H.

    2009-02-01

    Full Text Available Ružička opened the field of cyclic molecules such as cyclic terpenes and cyclic ketones with up to 17 ring atoms. This work until now was extended in many directions such as cyclic paraffins, crown ethers and cryptands and cyclic ester amides. Cyclic molecules are formed upon electron transfer and intramolecular association of polymers with two active ends and they are synthesized by directed cyclization of bifunctional macromolecules. In the course of step growth polymerization and ring opening polymerization, ring chain equilibria may be established; the larger the monomer unit the easier is the separation of pure oligomers such as the heptamer of cyclododecene with 84 carbon atoms in the ring. Still many questions remain open, in particular whether there are macrocyclic catenanes in commercial polycondensates.

  15. Macrocyclic polyether complexes of amino acids and amino acid salts

    International Nuclear Information System (INIS)

    Bidzilya, V.A.; Oleksenko, LP.

    1985-01-01

    This paper deals with the isolation of the complexes formed between various types of amino acid derivatives and macrocyclic polyethers, and the characterisation of their physical and chemical properties. The study shows that macrocyclic polyethers form 1:1 complexes with amino acids and amino acid derivatives, and that these complexes can be isolated in pure form. Amino acids can be bound to these complexes in their anionic forms, in switterionic forms, as well as in their protonated forms. These types of complexes may be useful for the transport of amino acids or their derivatives across both synthetic and natural membranes

  16. 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......, a precancerous skin condition. Metabolite profiling of various tissues of E. lathyris L. revealed that the mature seeds constituted a highly specialized tissue for the biosynthesis of lathyrane and ingenane diterpenoids. RNA–seq and transcriptome analysis of E. lathyris L. mature seeds followed by functional...

  17. 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)

  18. Macrocyclic olefin metathesis at high concentrations by using a phase-separation strategy.

    Science.gov (United States)

    Raymond, Michaël; Holtz-Mulholland, Michael; Collins, Shawn K

    2014-09-26

    Macrocyclic olefin metathesis has seen advances in the areas of stereochemistry, chemoselectivity, and catalyst stability, but strategies aimed at controlling dilution effects in macrocyclizations are rare. Herein, a protocol to promote macrocyclic olefin metathesis, one of the most common synthetic tools used to prepare macrocycles, at relatively high concentrations (up to 60 mM) is described by exploitation of a phase-separation strategy. A variety of macrocyclic skeletons could be prepared having either different alkyl, aryl, or amino acids spacers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Radiation chemistry of cis-syn-cis dicyclohexano-18-crown-6 (DCH18C6): Acidity and uranyl nitrate dependence

    Energy Technology Data Exchange (ETDEWEB)

    Draye, Micheline [Laboratoire de Chimie Moleculaire et Environnement (EA1651), Universite de Savoie-Polytech' Savoie, Campus Scientifique, 73376 Le Bourget du Lac Cedex (France)], E-mail: micheline.draye@univ-savoie.fr; Favre-Reguillon, Alain [Laboratoire de Chimie Organique (UMR7084), Conservatoire National des Arts et Metiers, 2 rue conte, 75003 Paris (France); Faure, Rene [Laboratoire des sciences analytiques, UMR CNRS 5180, Universite Claude Bernard, Lyon 1, 43 boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); Lemaire, Marc [Laboratoire de Catalyse et Synthese Organique, UMR CNRS 5246, Institut de Chimie et Biochimie Moleculaires et Supramoleculaires, Universite Lyon 1 CPE, 43 boulevard du 11 novembre 1918, Villeurbanne 69622 (France)

    2008-05-15

    The cis-syn-cis isomer of dicyclohexano-18-crown-6 (DCH18C6) has been shown to be an efficient extractant able to perform the separation of Pu(IV) and U(VI) from fission products and then the separation of Pu(IV) from U(VI) without valence exchange as required in the PUREX process. This macrocycle was irradiated in nitric acid with a {sup 137}Cs {gamma} source to study its radiation chemical stability. Radiation chemical yields (G) were determined by gas chromatography. The results show that the presence of uranyl nitrate has a strong influence on DCH18C6 radiation chemical stability. Indeed, the presence of this template ion increases the macrocycle stability by promoting fragments recombination.

  20. 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 ...

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

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 2. Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations. ANURADHA SANKARAN E J PADMA MALAR VENKATAPURAM RAMANUJAM ...

  2. Flexible macrocycles as versatile supports for catalytically active metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, JD; Gagnon, KJ; Teat, SJ; McIntosh, RD

    2016-02-12

    Here we present three structurally diverse clusters stabilised by the same macrocyclic polyphenol; t-butylcalix[8]arene. This work demonstrates the range of conformations the flexible ligand is capable of adopting, highlighting its versatility in metal coordination. In addition, a Ti complex displays activity for the ring-opening polymerisation of lactide

  3. 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 ...

  4. Crowned dens syndrome

    Directory of Open Access Journals (Sweden)

    Norma Belfiore

    2012-10-01

    Full Text Available Introduction Microcrystalline deposition in peri-odontoid articular structures is mainly responsible for acute or chronic cervical pain and is known as “crowned dens syndrome”.Materials and methods We described two cases of acute cervical pain associated with onset of fever and peripheral acute monoarthritis. Cervical computed tomography (CT scan showed linear calcification of the retrodens ligament and calcium pyrophosphate dehydrate (CPPD crystals were found in synovial fluid of inflamed joints. Both patients were treated with anti-inflammatory drugs and colchicine.Discussion Calcium depositions around the odontoid process of the axis can be occasionally detected by radiological studies. They are frequently asymptomatic but sometimes can be associated with severe neurological abnormalities, fever and acute neck pain. CPPD crystals are usually deposited in joints and bursae but occasionally can disrupt these anatomical confines and deposit in periarticular tissues, sometimes forming large masses confused with tumours.Conclusions Acute onset of cervical neck pain associated with elevation of inflammatory indicators and/or signs of cervical myelopathy should suggest CT scans searching for microcrystal depositions in the peryodonthoid tissue. Differential diagnosis of fever of unknown origin (FUO should include crowned dens syndrome specially in the elderly after exclusion of several endocrine or metabolic disorders, infection diseases (meningitis, arthritis (psoriatic arthritis and ankylosing spondylitis and tumours (chordoma, meningioma, osteoblastoma.

  5. 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

  6. Macrocyclic metal complexes for metalloenzyme mimicry and sensor development.

    Science.gov (United States)

    Joshi, Tanmaya; Graham, Bim; Spiccia, Leone

    2015-08-18

    Examples of proteins that incorporate one or more metal ions within their structure are found within a broad range of classes, including oxidases, oxidoreductases, reductases, proteases, proton transport proteins, electron transfer/transport proteins, storage proteins, lyases, rusticyanins, metallochaperones, sporulation proteins, hydrolases, endopeptidases, luminescent proteins, iron transport proteins, oxygen storage/transport proteins, calcium binding proteins, and monooxygenases. The metal coordination environment therein is often generated from residues inherent to the protein, small exogenous molecules (e.g., aqua ligands) and/or macrocyclic porphyrin units found, for example, in hemoglobin, myoglobin, cytochrome C, cytochrome C oxidase, and vitamin B12. Thus, there continues to be considerable interest in employing macrocyclic metal complexes to construct low-molecular weight models for metallobiosites that mirror essential features of the coordination environment of a bound metal ion without inclusion of the surrounding protein framework. Herein, we review and appraise our research exploring the application of the metal complexes formed by two macrocyclic ligands, 1,4,7-triazacyclononane (tacn) and 1,4,7,10-tetraazacyclododecane (cyclen), and their derivatives in biological inorganic chemistry. Taking advantage of the kinetic inertness and thermodynamic stability of their metal complexes, these macrocyclic scaffolds have been employed in the development of models that aid the understanding of metal ion-binding natural systems, and complexes with potential applications in biomolecule sensing, diagnosis, and therapy. In particular, the focus has been on "coordinatively unsaturated" metal complexes that incorporate a kinetically inert and stable metal-ligand moiety, but which also contain one or more weakly bound ligands, allowing for the reversible binding of guest molecules via the formation and dissociation of coordinate bonds. With regards to mimicking

  7. Host-guest complexation. 17. Design, syntheses, and complexation of macrocycles containing phosphoryl, pyridine oxide, and urea binding sites

    International Nuclear Information System (INIS)

    Kaplan, L.J.; Weisman, G.R.; Cram, D.J.

    1979-01-01

    Phosphoryl (P=O), urea (N 2 C=O), pyridine, and pyridine oxide (N → O) groups have been incorporated into the ring systems of macrocyclic polyethers. The association constants of the resulting eight new ligand systems toward Li + , Na + , K + , Rb + , Cs + , and NH 4 + picrates in CHCl 3 were surveyed, and the free energies of association were estimated. The P=O complexing sites were covalently bonded through two attached o-tolyl groups as in the unit RP(O)(C 6 H 4 CH 2 -o) 2 , in which different R groups were attached to phosphorus. The resulting unit, written as RPOD, was attached to two ether oxygens (0), which in turn were connected through CH 2 CH 2 or E units to form macrocycles. Ligand systems C 6 H 5 POD(OEOE) 2 O (9), C 6 H 5 POD(OEOEO) 2 E (10), o-HO 2 CC 6 H 4 POD(OEOE) 2 O (11), o-CH 3 O 2 CC 6 H 4 POD(OEOE) 2 O (12), CH 3 OPOD(OEOE) 2 O (13), and C 6 H 5 POD(OEO) 2 PODC 6 H 5 (14 and 15, the syn and anti isomers) were synthesized and examined. The urea complexing site was cyclic, CH 2 (CH 2 N) 2 C = O (abbreviated to UON), and was bonded through its two nitrogens to E units. The cycle prepared and examined was UON(EOEOE) 2 O (16). The pyridine and pyridine oxide complexing sites were bonded through CH 2 groups in their α,α' positions to comprise the units α-CH 2 (C 5 H 3 N)CH 2 -α and α-CH 2 (C 5 H 3 NO)CH 2 -α, respectively, the latter of which was abbreviated as POM. The new cycle prepared and examined was POM(OEOE) 2 O (18). The patterns of ΔG 0 values of complexation of these ligand systems were compared to those of 2,3-naphtho 18-crown-6 (19), 2,6-pyrido-18-crown-6 (20), and 1,3-benzo-18-crown-5 (21). The results suggest that those ligand systems whose organization of binding sites before and after complexation are the most similar show the highest structural recognition toward the anions

  8. 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.

  9. 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

  10. 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)

  11. Fluorescence Resonance Energy Transfer Systems in Supramolecular Macrocyclic Chemistry

    Directory of Open Access Journals (Sweden)

    Xin-Yue Lou

    2017-09-01

    Full Text Available The fabrication of smart materials is gradually becoming a research focus in nanotechnology and materials science. An important criterion of smart materials is the capacity of stimuli-responsiveness, while another lies in selective recognition. Accordingly, supramolecular host-guest chemistry has proven a promising support for building intelligent, responsive systems; hence, synthetic macrocyclic hosts, such as calixarenes, cucurbiturils, cyclodextrins, and pillararenes, have been used as ideal building blocks. Meanwhile, manipulating and harnessing light artificially is always an intensive attempt for scientists in order to meet the urgent demands of technological developments. Fluorescence resonance energy transfer (FRET, known as a well-studied luminescent activity and also a powerful tool in spectroscopic area, has been investigated from various facets, of which the application range has been broadly expanded. In this review, the innovative collaboration between FRET and supramolecular macrocyclic chemistry will be presented and depicted with typical examples. Facilitated by the dynamic features of supramolecular macrocyclic motifs, a large variety of FRET systems have been designed and organized, resulting in promising optical materials with potential for applications in protein assembly, enzyme assays, diagnosis, drug delivery monitoring, sensing, photosynthesis mimicking and chemical encryption.

  12. 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

  13. Comparison of classic and microwave-assisted synthesis of benzo-thio crown ethers, and investigation of their ion pair extractions

    Science.gov (United States)

    Calisir, Umit; Çiçek, Baki

    2017-11-01

    Macrocyclic benzo-thio crown ethers and benzo-oxo crown ethers were prepared using an esterification-ring closing method. These compounds were synthesised using 2,2‧-dithiodibenzoyl chloride, and various glycols and dithiols, in the presence of pyridine base under a nitrogen atmosphere in chloroform. All reactions were performed under reflux condition with conventional heating and microwave (MW) irradiation. The synthesised macrocycles were characterised by FT-IR, 1H NMR, 13C NMR, LC-MS, and elemental analysis methods. Extraction studies have been performed on these original macrocycles using liquid-liquid ion-pair extraction with Li+, Na+, K+, Ni2+, Ca2+, Mg2+, Zn2+, Fe2+,Fe3+, Co3+, Pb2+, Cr3+, Ag+, and Cd2+.The KD, ext.%, ΔG and log KExt values were also calculated. While (U1-U7) ligands exhibits selectivity for Zn2+, Ag+, Ca2+, Pb2+, Fe3+, Cr3+, Co2+, Mg2+, Cd2+, and Ni2+ metal salts, they showed no selectivity for Li+, K+ and Na+ metal salts. Furthermore, Fe3+is the most selective cation for all ligands for competitive extraction. We also observed that microwave heating can have certain benefits over conventional ovens: reaction rate acceleration, milder reaction conditions, higher chemical yield, and lower energy usage. These ligands could be used as metal sensors, enzyme inhibitors, antimicrobial/antifungal agents, and in biological applications.

  14. Kinetically E-selective macrocyclic ring-closing metathesis

    Science.gov (United States)

    Shen, Xiao; Nguyen, Thach T.; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization—a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl-B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib—a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis—was prepared by RCM carried out at a

  15. 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

  16. Hydrogen bond templated 1:1 macrocyclization through an olefin metathesis/hydrogenation sequence.

    Science.gov (United States)

    Trita, Andrada Stefania; Roisnel, Thierry; Mongin, Florence; Chevallier, Floris

    2013-07-19

    The construction of pyridine-containing macrocyclic architectures using a nonmetallic template is described. 4,6-Dichlororesorcinol was used as an exotemplate to self-organize two aza-heterocyclic units by OH···N hydrogen bonds. Subsequent sequential double olefin metathesis/hydrogenation reactions employing a single ruthenium-alkylidene precatalyst open access to macrocyclic molecules.

  17. Camelliin B and nobotanin I, macrocyclic ellagitannin dimers and related dimers, and their antitumor activity.

    Science.gov (United States)

    Yoshida, T; Chou, T; Haba, K; Okano, Y; Shingu, T; Miyamoto, K; Koshiura, R; Okuda, T

    1989-11-01

    Camelliin B and nobotanin I, dimeric hydrolyzable tannins of a new class having macrocyclic structures, were isolated from Camellia japonica and Heterocentron roseum, respectively. Nobotanin G and H of the structures related to nobotanin I, were also obtained from H. roseum. Camelliin B and also woodfordin C, a macrocyclic dimer from Woodfordia fruticosa, exhibited marked host-mediated antitumor activities.

  18. Molecular Assemblies of Porphyrins and Macrocyclic Receptors: Recent Developments in Their Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Abdirahman A. Mohamod

    2012-10-01

    Full Text Available Metalloporphyrins which form the core of many bioenzymes and natural light harvesting or electron transport systems, exhibit a variety of selective functional properties depending on the state and surroundings with which they exist in biological systems. The specificity and ease with which they function in each of their bio-functions appear to be largely governed by the nature and disposition of the protein globule around the porphyrin reaction center. Synthetic porphyrin frameworks confined within or around a pre-organized molecular entity like the protein network in natural systems have attracted considerable attraction, especially in the field of biomimetic reactions. At the same time a large number of macrocyclic oligomers such as calixarenes, resorcinarenes, spherands, cyclodextrins and crown ethers have been investigated in detail as efficient molecular receptors. These molecular receptors are synthetic host molecules with enclosed interiors, which are designed three dimensionally to ensure strong and precise molecular encapsulation/recognition. Due to their complex structures, enclosed guest molecules reside in an environment isolated from the outside and as a consequence, physical properties and chemical reactions specific to that environment in these guest species can be identified. The facile incorporation of such molecular receptors into the highly photoactive and catalytically efficient porphyrin framework allows for convenient design of useful molecular systems with unique structural and functional properties. Such systems have provided over the years attractive model systems for the study of various biological and chemical processes, and the design of new materials and molecular devices. This review focuses on the recent developments in the synthesis of porphyrin assemblies associated with cyclodextrins, calixarenes and resorcinarenes and their potential applications in the fields of molecular encapsulation/recognition, and

  19. 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.

  20. 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)

  1. 8th International Symposium on Supramolecular and Macrocyclic Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Jeffery T. [Univ. of Maryland, College Park, MD (United States)

    2015-09-18

    This report summarizes the 8th International Conference on Supramolecular and Macrocyclic Chemistry (ISMSC-8). DOE funds were used to make it more affordable for students, post-docs and junior faculty to attend the conference by covering their registration costs. The conference was held in Crystal City, VA from July 7-11, 2013. See http://www.indiana.edu/~ismsc8/ for the conference website. ISMSC-8 encompassed the broad scope and interdisciplinary nature of the field. We met our goal to bring together leading scientists in molecular recognition and supramolecular chemistry. New research directions and collaborations resulted this conference. The DOE funding was crucial for us achieving our primary goal.

  2. 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)

  3. 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...... programme includes variations of the sea state parameters and of the geometrical configuration of the breakwater and crown wall. Basic relations between forces/overtopping and the varied parameters are examined and preliminary design guidelines for structures within the tested range of variations...

  4. Photoresponsive Amphiphilic Macrocycles Containing Main-Chain Azobenzene Polymers.

    Science.gov (United States)

    Sun, Yadong; Wang, Zhao; Li, Yiwen; Zhang, Zhengbiao; Zhang, Wei; Pan, Xiangqiang; Zhou, Nianchen; Zhu, Xiulin

    2015-07-01

    Herein, the first example of photosensitive cyclic amphiphilic homopolymers consisting of multiple biphenyl azobenzene chromophores in the cyclic main chain tethered with hydrophilic tetraethylene glycol monomethyl ether units is presented. The synthetic approach involves sequentially performed thermal catalyzed "click" step-growth polymerization in bulk, and Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) intramolecular cyclization from α-alkyne/ω-azide linear precursors. It is observed that such amphiphilic macrocycles exhibit increased glass transition temperatures (Tg ), slightly faster trans-cis-trans photoisomerization, and enhanced fluorescence emission intensity compared with the corresponding linear polymers. In addition, the cyclic amphiphilic homopolymers self-assemble into spherical nanoparticles with smaller sizes which possess slower photoresponsive behaviors in a tetrahydrofuran/water mixture compared with those of the linear ones. All these interesting observations suggest that the cyclic topology has a great influence on the physical properties and self-assembly behavior of these photoresponsive amphiphilic macrocycles in general. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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

  6. 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.

  7. 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...

  8. Removal of failed crown and bridge

    OpenAIRE

    Sharma, Ashu; Rahul, G.R.; Poduval, Soorya T.; Shetty, Karunakar

    2012-01-01

    Crown and bridge have life span of many years but they fail for a number of reasons. Over the years, many devices have been designed to remove crowns and bridges from abutment teeth. While the removal of temporary crowns and bridges is usually very straightforward, the removal of a definitive cast crown with unknown cement is more challenging. Removal is often by destructive means. There are a number of circumstances, however, in which conservative disassembly would aid the practitioner in co...

  9. Equations to convert compacted crown ratio to uncompacted crown ratio for trees in the Interior West

    Science.gov (United States)

    Chris Toney; Matthew C. Reeves

    2009-01-01

    Crown ratio is the proportion of total tree length supporting live foliage. Inventory programs of the US Forest Service generally define crown ratio in terms of compacted or uncompacted measurements. Measurement of compacted crown ratio (CCR) involves envisioning the transfer of lower branches of trees with asymmetric crowns to fill holes in the upper portion of the...

  10. Methods and intermediates for the synthesis of dipyrrin-substituted porphyrinic macrocycles

    Science.gov (United States)

    Yu, Lianhe; Muthukumaran, Kannan; Sreedharan, Prathapan; Lindsey, Jonathan S.

    2010-05-25

    The present invention provides dipyrrin substituted porphyrinic macrocycles, intermediates useful for making the same, and methods of making the same. Such compounds may be used for purposes including the making of molecular memory devices, solar cells and light harvesting arrays.

  11. Surface enhanced second harmonic generation from macrocycle, catenane, and rotaxane thin films : Experiments and theory

    NARCIS (Netherlands)

    Arfaoui, I.; Bermudez, V.; Bottari, G.; De Nadai, C.; Jalkanen, J.P.; Kajzar, F.; Leigh, D.A.; Lubomska, M.; Mendoza, S.M.; Niziol, J.; Rudolf, Petra; Zerbetto, F.

    2006-01-01

    Surface enhanced second harmonic generation (SE SHG) experiments on molecular structures, macrocycles, catenanes, and rotaxanes, deposited as monolayers and multilayers by vacuum sublimation on silver, are reported. The measurements show that the molecules form ordered thin films, where the highest

  12. Surface enhanced SHG from macrocycle, catenane and rotaxane thin films : experiments and theory.

    NARCIS (Netherlands)

    Arfaoui, I.; Bermudez, V.; De Nadai, C.; Jalkanen, J.-P.; Kajzar, F.; Leigh, D.A.; Lubomska, M.; Mendoza, S.M.; Niziol, J.; Rudolf, Petra; Zerbetto, F.; Grote, JG; Kaino, T; Kajzar, F

    2005-01-01

    Surface enhanced second harmonic generation experiments on supramolecules: macrocycles, catenanes and rotaxanes, monolayers and multilayers deposited by vacuum evaporation on silver layers are reported and described. The measurements show that the molecules are ordered in thin films. The highest

  13. 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.

  14. 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...

  15. Solvent extraction of europium trifluoromethanesulfonate into nitrobenzene by using some electroneutral macrocyclic lactam receptors

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

    Roč. 293, č. 2 (2012), s. 699-702 ISSN 0236-5731 Institutional support: RVO:61389013 Keywords : europium * macrocyclic lactam receptors * extraction and stability constants Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.467, year: 2012

  16. 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

  17. Macrocyclic bis-quinolizidine alkaloids from Xestospongia muta.

    Science.gov (United States)

    Dung, Duong Thi; Hang, Dan Thi Thuy; Yen, Pham Hai; Quang, Tran Hong; Nhiem, Nguyen Xuan; Tai, Bui Huu; Minh, Chau Van; Kim, Youn-Chul; Kim, Dong Cheol; Oh, Hyuncheol; Kiem, Phan Van

    2018-03-29

    A new stereoisomer Meso-araguspongine C together with nine reported macrocyclic bis-quinolizidine alkaloids araguspongines A, C, E, L, N-P, petrosin, and petrosin A were isolated from marine sponge Xestospongia muta. Stereochemistry of meso-araguspongine C (2) and araguspongines N-P (3-5) were established by their NMR data and conformational analyses. Both araguspongine C (1) and meso-araguspongine C (2) exhibited great cytotoxic activity towards HepG-2, HL-60, LU-1, MCF-7, and SK-Mel-2 human cancer cells (IC 50 in the range of 0.43-1.02 μM). At a concentration of 20 μM, isolated compounds (1-10) also showed modest inhibitory effects (from 7.6 to 40.8%) on the NO production in LPS activated RAW264.7 macrophages.

  18. 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

  19. 1H NMR study on the intermolecular interactions of macrocyclic and single α-amino acids

    Science.gov (United States)

    Quevedo, Rodolfo; Pabón, Laura; Quevedo-Acosta, Yovanny

    2013-06-01

    Through analysis of 1H NMR spectra, evidence was found for intermolecular interactions between macrocyclic amino acid derivatives from L-tyrosine and their importance in the formation of aggregates in solution. It was also shown that both macrocyclic and simple amino acids are capable of retaining alcohol molecules through hydrogen bonding, where the alcohol molecule acts as a proton donor and the amino group acts as an acceptor.

  20. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach.

    Science.gov (United States)

    Mangold, Shane L; Grubbs, Robert H

    2015-08-01

    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E - and Z- olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E - or Z -olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

  1. 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...

  2. Crown structure of Picea omorika trees in the plantation

    OpenAIRE

    Krstić M.; Stavretović N.; Isajev V.; Bjelanović I.

    2012-01-01

    The study was carried out in Serbian spruce (Picea omorika Panč/Purkynĕ) plantations in the western Serbia. The paper presents results of the analysis of crown development. The following elements were analyzed: total tree height, height of the crown base, absolute and relative crown length, maximal crown diameter, coefficient of crown spreading and degree of crown girth. We discuss approaches to the modeling of tree crown growth and development, growing under favorable environmental and...

  3. 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.

  4. 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.

  5. Fracture resistance of various temporary crown materials.

    Science.gov (United States)

    Yilmaz, Asude; Baydaş, Seyfettin

    2007-01-01

    The aim of this study was to evaluate the fracture resistance of various provisional crown materials using an in vitro model test system. In the present study polycarbonate crowns, prefabricated by the manufacturer (3M Polycarbonate Crown), and the temporary crowns, fabricated in the dental laboratory environment, were fabricated using bis-acryl composite (Protemp II), autopolymerizing PMMA resin (BISICO Temp S), and heat-polymerized PMMA resin (Major C&B-V Dentine). All temporary crowns were stored in distilled water for 24 hours at room temperature prior to testing. The crowns were seated on metal dies, fabricated from Cr-Co alloy (AZ Dental, Konstanz, Germany), and then tested using the indenter of a Hounsfield testing machine (Hounsfield Tensometer, Hounsfield Test Equipment, Raydon, England). The tip of the indenter was located at a position one-third of the way down the inciso-palatine surface at 135 masculine. The data were statistically analyzed for differences using one-way analysis of variance (ANOVA) and the Tukey HSD test (P crowns were significantly different from the BISICO Temp S, Protemp II, and Major C&B-V Dentine (P crowns may be preferable to the other types of temporary crowns used in this study.

  6. 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.

  7. COMPARATIVE ANALYSIS OF THE REPS NUMBER WITHIN TWO TRAINING MACROCYCLES OF THE WEIGHTLIFTING OLYMPIC TEAM

    Directory of Open Access Journals (Sweden)

    ULĂREANU MARIUS VIOREL

    2010-12-01

    Full Text Available The authors present a comparative analysis of the number of repetitions in two training macro-cycles of the weightlifting Olympic team. We have considered that the differences between the number of reps in each training stage of the macro-cycles no. 1 and 2 will influence the performances achieved in competition. This approach has led to the organization of a study group in the weightlifting Olympic team of Romania. The scientific argument is the presentation of the number of reps during the preparation of the weightlifting Olympic team in different mezzo and micro-cycles of training, that, by decreasing the number of reps and increasing the intensity of the effort up to the maximum level from a training micro-cycle to another,contributes to reaching the fitness peak in competitive period within the macro-cycle no.1; also, an optimum number of reps during the training macro-cycle no.2 will make possible to keep the fitness necessary for their turning into good account in the next competition.The study was conducted over a period of two training macro-cycles (04.01-16.08.2008, with a group of 6 athletes, of 17 to 31 years old, whose target of performance was the participation in the EuropeanChampionships (E. C. for Seniors, Lignano – Sabbiadoro, Italy 2008 and the Olympic Games (J.O. in Beijing in 2008. The athletes’ progresses during the training stages and competitions were recorded by means of the statistical-mathematical and plotting methods.The study highlights the number of reps within two training macro-cycles of the weightlifting Olympic team. At the end of the paper we are able to confirm that the differences between the number of reps at each stage of training in the macro-cycles no. 1 and 2 have influenced the performances achieved in competition

  8. Metal Complexes with a Hexadentate Macrocyclic Diamine-Tetracarbene Ligand.

    Science.gov (United States)

    Lu, Taotao; Yang, Chu-Fan; Zhang, Li-Yi; Fei, Fan; Chen, Xue-Tai; Xue, Zi-Ling

    2017-10-02

    A hexadentate macrocyclic N-heterocyclic carbene (NHC) ligand precursor (H 4 L)(PF 6 ) 4 containing four benzimidazolium and two secondary amine groups, has been synthesized and characterized. Coordination chemistry of this new macrocyclic diamine-tetracarbene ligand has been studied by the synthesis of its Ag(I), Au(I), Ni(II), and Pd(II) complexes. Reactions of (H 4 L)(PF 6 ) 4 with different equiv of Ag 2 O result in Ag(I) complexes [Ag(H 2 L)](PF 6 ) 3 (1) and [Ag 2 (H 2 L)](PF 6 ) 4 (2). A mononuclear Au(I) complex [Au(H 2 L)](PF 6 ) 3 (3) and a trinuclear Au(I) complex [Au 3 (H 2 L)(Cl) 2 ](PF 6 ) (4) are obtained by transmetalation of 1 and 2 with AuCl(SMe 2 ), respectively. Reactions of (H 4 L)(PF 6 ) 4 with Ni(OAc) 2 and Pd(OAc) 2 in the presence of NaOAc yield [Ni(L)](PF 6 ) 2 (5) and [Pd(L)](PF 6 ) 2 (6), respectively, containing one Ni(II) and Pd(II) ion with distorted square-planar geometry. Using more NaOAc results in the formation of unusual dinuclear complexes [Ni 2 (L-2H)](PF 6 ) 2 (7) and [Pd 2 (L-2H)](PF 6 ) 2 (8) (L-2H = deprotonated ligand after removing two H + ions from two secondary amine groups in L), respectively, featuring a rare M 2 N 2 core formed by two bridging amides. 7 is also formed by the reaction of 5 with 1.0 equiv of Ni(OAc) 2 ·4H 2 O in the presence of NaOAc. Transmetalation of 2 with 2.0 equiv of Ni(PPh 3 ) 2 Cl 2 gives [Ni 2 (L)(μ-O)](PF 6 ) 2 (9), the first example of a dinuclear Ni(II) complex with a singly bridging oxo group. 9 is converted to 7 in good yield through the treatment with NaOAc.

  9. 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.

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

    African Journals Online (AJOL)

    Four crown dimensions (crown diameter, crown projection area, crown length and crown ratio) were each incorporated into nonlinear individual tree total height and basal area increment models for African white wood (Triplochiton scleroxylon K. Schum). The basic height/basal area growth model was formulated as a ...

  11. Equations for predicting uncompacted crown ratio based on compacted crown ratio and tree attributes.

    Science.gov (United States)

    Vicente J. Monleon; David Azuma; Donald. Gedney

    2004-01-01

    Equations to predict uncompacted crown ratio as a function of compacted crown ratio, tree diameter, and tree height are developed for the main tree species in Oregon, Washington, and California using data from the Forest Health Monitoring Program, USDA Forest Service. The uncompacted crown ratio was modeled with a logistic function and fitted using weighted, nonlinear...

  12. 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.

  13. Dermatobia hominis: Potencial risk of resistance to macrocyclic lactones.

    Science.gov (United States)

    das Neves, José Henrique; Carvalho, Nadino; Amarante, Alessandro F T

    2015-09-15

    Dermatobia hominis is an ectoparasite that infests various species of mammals, including cattle, impairing the quality of cowhides and leather. After observing natural infestation with D. hominis larvae in cattle on two farms in the state of São Paulo, Brazil, we evaluated the efficacy of two macrocyclic lactones, ivermectin and moxidectin, against this parasite. The drugs were administered to 10 animals in each group, following the manufacturer's instructions. The groups were: Group 1-treated with ivermectin (0.2mg/kg of body weight (BW)); Group 2-treated with moxidectin (0.2mg/kg BW); and Group 3-control (untreated). On the farm in Pardinho, a total of 12 and 16 live larvae were found in 6 and in 8 animals 10 days after the treatment with ivermectin and moxidectin, respectively, while in the control group 4 bovines had a total of 7 live larvae. On the farm in Anhembi, 2, 4 and 6 live larvae were extracted from ivermectin, moxidectin and control groups, respectively, after the treatment. This is the first report of the presence of live D. hominis larvae after the treatment of cattle with ivermectin and moxidectin in Brazil. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Benjamin Riss-Yaw

    2017-11-01

    Full Text Available 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.

  15. 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.

  16. Unsaturated 15 and 16 Membered Appended Naphthalene Macrocyclic Molecules for The Development of Fluorometric Chemosensors

    Science.gov (United States)

    Hasan, S.; Salleh, S.; Hamdan, S.; Yamin, B.

    2017-02-01

    Unsaturated macrocyclic molecules have got an interest due to their potential in catalysis, ion exchange and electron transfer. Salicaldehyde derivatives macrocyclic molecules have a broad range in synthesis. In this study, two unsaturated macrocyclic molecules (L1 and L2) have been synthesized. The preparation of unsaturated macrocyclic ligands involve two steps; the reaction of salicylaldehyde with 1,2-dibromoethane or 1,4-dibromobutane to produce precursor, then cyclisation were completed using schiff base technique by adding diamines (naphthalene diamine). The ligands were characterized spectroscopically. In FT-IR spectrums, the form of the ligands mainly can be observed on the disappearance of the carbonyl group of aldehyde at approximately 1650cm-1 that was readily assigned to C=O group of salicylaldehyde with the replacement of C=N peak at 1684.13cm-1. The success in producing macrocyclic ligands have been further characterized using fluorescence emission spectroscopy (FES) and revealed the typical emission of naphthalene at ∼430nm. Fluorescence changes of L1 and L2 showed high selectivity for Fe3+ and Cu2+ respectively in the presence of other common metal ions, such as Zn2+, Ni2+ and Co2+. Besides, the ligand was sensitive enough to detect the concentration of ferric ion with the detection limit down to 1.08 x 10-6 M and fluorescence change that was unaffected by the presence of other common coexisting metal ions. Complexation with Co(II) was also attempted.

  17. ConfBuster: Open-Source Tools for Macrocycle Conformational Search and Analysis

    Directory of Open Access Journals (Sweden)

    Xavier Barbeau

    2018-01-01

    Full Text Available Macrocycles are cyclic macromolecules that have gained an increased interest in drug development. To our knowledge, the current bioinformatics tools that are available to investigate and predict macrocycles 3D conformations are limited in their availability. In this paper, we introduce ConfBuster, a suite of tools written in Python with the goal of sampling the lower energy conformations of macrocycles. The suite also includes tools for the analysis and visualisation of the conformational search results. Coordinate sets of single molecules in MOL2 or PDB format are required as input, and a set of lower energy conformation coordinates is returned as output, as well as PyMOL script and graphics for results analysis. In addition to Python and the optional R programming languages with freely available packages, the tools require Open Babel and PyMOL to work properly. For several examples, ConfBuster found macrocycle conformations that are within few tenths of Å of the experimental structures in minutes. To our knowledge, this is the only open-source tools for macrocycle conformational search available to the scientific community

  18. FRACTURE-RESISTANT MONOLITHIC DENTAL CROWNS

    Science.gov (United States)

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

    2016-01-01

    Objective To quantify the splitting resistance of monolithic zirconia, lithium disilicate and nanoparticle-composite dental crowns. Methods 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. Results 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. Significance 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. PMID:26792623

  19. 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.

  20. Fracture resistance of zirconia-composite veneered crowns in comparison with zirconia-porcelain crowns.

    Science.gov (United States)

    Alsadon, Omar; Patrick, David; Johnson, Anthony; Pollington, Sarah; Wood, Duncan

    2017-05-31

    The objectives were to evaluate the fracture resistance and stress concentration in zirconia/composite veneered crowns in comparison to zirconia/porcelain crowns using occlusal fracture resistance and by stress analysis using finite element analysis method. Zirconia substructures were divided into two groups based on the veneering material. A static load was applied occlusally using a ball indenter and the load to fracture was recorded in Newtons (N). The same crown design was used to create 3D crown models and evaluated using FEA. The zirconia/composite crowns subjected to static occlusal load showed comparable results to the zirconia/porcelain crowns. Zirconia/composite crowns showed higher stress on the zirconia substructure at 63.6 and 50.9 MPa on the zirconia substructure veneered with porcelain. In conclusion, zirconia/composite crowns withstood high occlusal loads similar to zirconia/porcelain crowns with no significant difference. However, the zirconia/composite crowns showed higher stress values than the zirconia/porcelain crowns at the zirconia substructure.

  1. Comparison of internal fit between implant abutments and cast metal crowns vs laser-sintered crowns.

    Science.gov (United States)

    Kiliçarslan, Mehmet Ali; Özkan, Pelin; Uludag, Bülent; Mumcu, Emre

    2014-07-01

    A common problem related to cemented single crowns is the internal misfit, which may cause inadequate retention, especially when seated on the implant abutment. The aim of this study was to compare the internal fit of Co-Cr crowns using a traditional lost-wax casting technique from laser-sintered Co-Cr alloy crowns. Twelve metallic crowns per each technique were fabricated. The effect of the thickness of cement, originated internal gap was evaluated. Crowns were cemented on the implant abutments with resin cement, and the internal fit of crowns was measured at five areas with an optical microscope. The data were analyzed, and the means were compared with a t-test (pcrowns obtained through the lost wax method (min. 65.50 ± 9.54 μm and max. 313.46 ± 48.12 μm). The fit of the metal crown likely varies with the fabrication technique. The use of techniques that enable the adjustment of crown parameters, such as the laser sintering technique, maintains the desired fit between casting and implant abutments. This study investigated which technique affects the internal fit of cemented implant-supported crowns, comparing the use of lost wax casting and laser-sintered metal dental alloys. The results of this study indicate that the use of laser-sintered crowns can improve for crown accuracy.

  2. Lava zirconia crowns and bridges.

    Science.gov (United States)

    Suttor, D

    2004-01-01

    Ceramic restorations--suitable for the anterior as well as the posterior region, simultaneously satisfying the demand for high strength, longevity, and esthetics--are an increasingly important field for the dental professional. Because of its outstanding mechanical properties and esthetics with a proven track record in other industrial areas, zirconium oxide (zirconia) is emerging in the dental industry. As the manufacturing method of choice, CAD/CAM is important for the dental laboratory; however, in the final analysis, the primary focus will be on the material properties and the clinical performance of the result of the CAD/CAM process--in this case, zirconia crowns and bridges. This is especially true since some concepts do not require the acquisition of a CAD/CAM system at all.

  3. Fracture resistance of different primary anterior esthetic crowns

    OpenAIRE

    Al Shobber, Manar Zaki; Alkhadra, Thamer A.

    2017-01-01

    Purpose: Investigate and compare fracture resistance of four commercially available esthetic crowns. Methods: Sixty-four anterior crowns were used: NuSmile Primary crowns (NuSmile, Houston, Tex. USA) (16); Preveneered Cheng Crowns, (Orthodontic Technologies Inc., Houston, TX) (16); NuSmile ZR (NuSmile, Houston, Tex. USA); and Cheng Crowns zirconia (Orthodontic Technologies Inc., Houston, TX). Crowns were mounted and cemented on a negative replica and placed under servo hydraulic mechanical...

  4. 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.

  5. 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.

  6. 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

  7. Donor-Acceptor Conjugated Macrocycles: Synthesis and Host-Guest Coassembly with Fullerene toward Photovoltaic Application.

    Science.gov (United States)

    Zhang, Si-Qi; Liu, Zhen-Yu; Fu, Wei-Fei; Liu, Feng; Wang, Chuan-Ming; Sheng, Chun-Qi; Wang, Yi-Fei; Deng, Ke; Zeng, Qing-Dao; Shu, Li-Jin; Wan, Jun-Hua; Chen, Hong-Zheng; Russell, Thomas P

    2017-11-28

    Electron-rich (donor) and electron-deficient (acceptor) units to construct donor-acceptor (D-A) conjugated macrocycles were investigated to elucidate their interactions with electron-deficient fullerene. Triphenylamine and 4,7-bisthienyl-2,1,3-benzothiadiazole were alternately linked through acetylene, as the donor and acceptor units, respectively, for pentagonal 3B2A and hexagonal 4B2A macrocycles. As detected by scanning tunneling microscopy, both D-A macrocycles were found to form an interesting concentration-controlled nanoporous monolayer on highly oriented pyrolytic graphite, which could effectively capture fullerene. Significantly, the fullerene filling was cavity-size-dependent with only one C 70 or PC 71 BM molecule accommodated by 3B2A, while two were accommodated by 4B2A. Density functional theory calculations were also utilized to gain insight into the host-guest systems and indicted that the S···π contact is responsible for stabilizing these host-guest systems. Owing to the ellipsoidal shape of C 70 , C 70 molecules are standing or lying in molecular cavities depending on the energy optimization. For the 3B2A/PC 71 BM blended film, PC 71 BM was intercalated into the cavity formed by the macrocycle 3B2A and provided excellent power conversion efficiency despite the broad band gap (2.1 eV) of 3B2A. This study of D-A macrocycles incorporating fullerene provides insights into the interaction mechanism and electronic structure in the host-guest complexes. More importantly, this is a representative example using D-A macrocycles as a donor to match with the spherical fullerene acceptor for photovoltaic applications, which offer a good approach to achieve molecular scale p-n junctions for substantially enhanced efficiencies of organic solar cells through replacing linear polymer donors by cyclic conjugated oligomers.

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

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.

    1993-12-31

    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.

  9. Design and synthesis of a new steroid-macrocyclic derivative with biological activity.

    Science.gov (United States)

    López-Ramos, Maria; Figueroa-Valverde, Lauro; Herrera-Meza, Socorro; Rosas-Nexticapa, Marcela; Díaz-Cedillo, Francisco; García-Cervera, Elodia; Pool-Gómez, Eduardo; Cahuich-Carrillo, Regina

    2017-04-01

    The aims of this study were to evaluate the positive inotropic effect of a new macrocyclic derivative (compound 11 ) and characterize the molecular mechanism involved in its biological activity. The first step was achieved by synthesis of a macrocyclic derivative involving a series of reactions for the preparation of several steroid derivatives such as (a) steroid-pyrimidinone ( 3 and 4 ), (b) steroid-amino ( 5 ), (c) steroid-imino ( 6 ), (d) ester-steroid ( 7 and 8 ), and (e) amido-steroid ( 9 and 10 ). Finally, 11 was prepared by removing the tert -butyldimethylsilane fragment of 10 . The biological activity of compounds on perfusion pressure and vascular resistance was evaluated on isolated rat heart using the Langendorff model. The inotropic activity of 11 was evaluated in presence of prazosin, metoprolol, indomethacin, nifedipine, and flutamide to characterize its molecular mechanism. Theoretical experiments were carried out with a Docking model, to assess potential interactions of androgen receptor with 11 . The results showed that only this macrocyclic derivative exerts changes on perfusion pressure and vascular resistance translated as the positive inotropic effect, and this effect was blocked with flutamide; these data indicate that the positive inotropic activity induced by this macrocyclic derivative was via androgen receptor activation. The theoretical results indicated that the interaction of the macrocyclic derivative with the androgen receptor involves several amino acid residues such as Leu 704 , Asn 705 , Met 780 , Cys 784 , Met 749 , Leu 762 , Phe 764 , Ser 778 , and Met 787 . In conclusion, all these data suggest that the positive inotropic activity of the macrocyclic derivative may depend on its chemical structure.

  10. COMPARATIVE ANALYSIS OF THE REPS NUMBER WITHIN TWO TRAINING MACROCYCLES OF THE WEIGHTLIFTING OLYMPIC TEAM

    OpenAIRE

    ULĂREANU MARIUS VIOREL; POTOP VLADIMIR

    2010-01-01

    The authors present a comparative analysis of the number of repetitions in two training macro-cycles of the weightlifting Olympic team. We have considered that the differences between the number of reps in each training stage of the macro-cycles no. 1 and 2 will influence the performances achieved in competition. This approach has led to the organization of a study group in the weightlifting Olympic team of Romania. The scientific argument is the presentation of the number of reps during the ...

  11. Macrocyclic prolinyl acyl guanidines as inhibitors of β-secretase (BACE).

    Science.gov (United States)

    Boy, Kenneth M; Guernon, Jason M; Wu, Yong-Jin; Zhang, Yunhui; Shi, Joe; Zhai, Weixu; Zhu, Shirong; Gerritz, Samuel W; Toyn, Jeremy H; Meredith, Jere E; Barten, Donna M; Burton, Catherine R; Albright, Charles F; Good, Andrew C; Grace, James E; Lentz, Kimberley A; Olson, Richard E; Macor, John E; Thompson, Lorin A

    2015-11-15

    The synthesis, evaluation, and structure-activity relationships of a class of acyl guanidines which inhibit the BACE-1 enzyme are presented. The prolinyl acyl guanidine chemotype (7c), unlike compounds of the parent isothiazole chemotype (1), yielded compounds with good agreement between their enzymatic and cellular potency as well as a reduced susceptibility to P-gp efflux. Further improvements in potency and P-gp ratio were realized via a macrocyclization strategy. The in vivo profile in wild-type mice and P-gp effects for the macrocyclic analog 21c is presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Short communication: Macrocyclic lactone residues in butter from Brazilian markets.

    Science.gov (United States)

    Macedo, Fabio; Marsico, Eliane Teixeira; Conte-Júnior, Carlos Adam; de Almeida Furtado, Leonardo; Brasil, Taila Figueredo; Pereira Netto, Annibal Duarte

    2015-06-01

    Macrocyclic lactones (ML) are commonly used in drug formulations for the treatment of parasites in cattle. In Brazil, except for drugs (or formulations) with long-term (half-life) effects, ML are registered for use in bovines. Indiscriminate use of ML may result in the presence of residues in milk and dairy products due to their lipophilic properties and thermal stability. This study applied a method of liquid chromatography with fluorimetric detection, recently developed and validated for the determination of residues of abamectin, doramectin, ivermectin, and moxidectin in butter. The method was applied to 38 samples of commercial butter purchased in the metropolitan area of Rio de Janeiro, Brazil, between June and September 2013, analyzed in triplicate. Ivermectin was detected in 89.5% of the samples, with concentrations between 0.3 and 119.4 µg/kg; 76.3% of the samples contained doramectin (0.6 to 64.7 µg/kg) and 55.2% contained abamectin (0.7 to 4.5 µg/kg). Most butter samples (76.3%) contained residues of more than 1 ML; however, no residues of moxidectin were detected. The results showed a high incidence of the presence of avermectins in butter samples. Butter is not included in the Brazilian National Plan for Control of Residues and Contaminants in Animal Products. As ML residues concentrate in lipophilic compounds, butter and other fatty dairy products should be screened for the presence of ML residues. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  13. 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.

  14. Marginal Strength of Collarless Metal Ceramic Crown

    Directory of Open Access Journals (Sweden)

    Sikka Swati

    2010-01-01

    fracture strength at margins of metal ceramic crowns cemented to metal tooth analogs. Crowns evaluated with different marginal configurations, shoulder and shoulder bevel with 0 mm, 0.5 mm, 1 mm, and 1.5 mm, were selected. Methods. Maxillary right canine typhodont tooth was prepared to receive a metal ceramic crown with shoulder margin. This was duplicated to get 20 metal teeth analogs. Then the same tooth was reprepared to get shoulder bevel configuration. These crowns were then cemented onmetal teeth analogs and tested for fracture strength atmargin on an Instron testing machine. A progressive compressive load was applied using 6.3 mm diameter rod with crosshead speed of 2.5 mm per minute. Statisticaly analysis was performed with ANOVA, Student's “t” test and “f” test. Results. The fracture strength of collarless metal ceramic crowns under study exceeded the normal biting force. Therefore it can be suggested that collarless metal ceramic crowns with shoulder or shoulder bevel margins up to 1.5 mm framework reduction may be indicated for anteriormetal ceramic restorations. Significance. k Collarless metal ceramic crowns have proved to be successful for anterior fixed restorations. Hence, it may be subjected to more clinical trials.

  15. Colorimetric values of esthetic stainless steel crowns.

    Science.gov (United States)

    Hosoya, Yumiko; Omachi, Koichi; Staninec, Michal

    2002-01-01

    The colorimetric values of two different kinds of esthetic stainless steel crowns were measured and compared with the colorimetric values of primary anterior teeth in Japanese children. The colorimetric values of resin composite-faced stainless steel crowns (Kinder Krown) and epoxy-coated stainless steel crowns (White Steel Crown) were measured with a color difference meter. The Commission Internationale de Eclairage L*, a*, b*, and delta E*ab values and Munsell value, chroma, and hue were calculated. The data were compared with previously reported colorimetric values of Japanese primary anterior teeth measured with the same color difference meter used in this study. Compared to Japanese primary anterior teeth, Kinder Krown Pedo I and Pedo II showed much higher L* values and lower hue; on the other hand, White Steel Crown showed much higher L*, a*, b* values, much higher value and chroma, and much lower hue. Color analysis revealed that the colors of the White Steel Crown and Kinder Krown Pedo I were substantially different from the color of Japanese primary anterior teeth. The color difference between Pedo II crowns and Japanese primary anterior teeth was relatively high, but the color of Pedo II might be acceptable for clinical use.

  16. Synthesis of novel macrocycles carrying pincer-type ligands as future candidates for potential applications in size-selective, stereochemical and recyclable catalysts

    Science.gov (United States)

    Khan, Burhan; Shah, Muhammad Raza; Rabnawaz, Muhammad

    2018-03-01

    Macrocycles with ultra dense functionalities are very useful but are difficult to synthesize. In this study, we report six novel macrocycles bearing a pincer ligand alone or a combination of pincer-calixarenes, and pincer-fluorene moieties. Click chemistry was utilized to synthesize the desired macrocycles in good yields. These macrocycles were fully characterized using mass spectrometry (EI-MS, ESI-MS, and MALDI-TOF MS), and NMR spectroscopy. These macrocycles are under investigations as size-selective and recyclable catalysts for various chemical transformations.

  17. Retention and surface changes of zirconia primary crowns with secondary crowns of different materials.

    Science.gov (United States)

    Turp, Işıl; Bozdağ, Ergün; Sünbüloğlu, Emin; Kahruman, Cem; Yusufoğlu, Ibrahim; Bayraktar, Gülsen

    2014-11-01

    To evaluate zirconia as a substitute for gold alloy in primary crowns facing secondary crowns manufactured with different materials, in terms of long-term retention force changes, wear, and phase transformation was aimed. A total of 12 groups, each containing six samples, consisting of gold alloy primary crown-electroformed gold secondary crowns (AA), zirconia primary crown-electroformed gold secondary crowns (ZA) and zirconia primary crown-casted non-precious alloy secondary crowns (ZC) with conus angles of 0°, 2°, 4°, and 6° were evaluated. Samples were subjected to 10,000 insertion-separation cycles in artificial saliva and retention force was measured. X-ray diffraction and scanning electron microscope analysis were performed on the sample surfaces. The highest retention forces were obtained from ZC-0° group (72.09-71.26 N) and the lowest were obtained from ZA-4° (12.73-19.44 N) and ZA-6° (5.36-19.73 N) groups in the beginning and after 10,000 cycles, respectively. Retention force increased as the conus angle decreased. The monoclinic phase ratio of the zirconia primary crowns decreased after the experiments. No wear was observed in zirconia primary crowns except for the ZC-0° and ZC-2° groups. The use of zirconia primary crowns resulted in a less excursive retention force. A more predictable and less excursive retention force can be obtained using a hard and rigid primary crown material like zirconia. Despite a lack of knowledge about the aging of zirconia without a veneer layer in the oral environment, zirconia primary crowns are more advantageous in terms of retention force development and wear.

  18. Internal fit evaluation of crowns prepared using a new dental crown fabrication technique: laser-sintered Co-Cr crowns.

    Science.gov (United States)

    Ucar, Yurdanur; Akova, Tolga; Akyil, Musa S; Brantley, William A

    2009-10-01

    Difficulties encountered during casting of base metal dental alloys limit their use. Application of these alloys might be enhanced if new techniques are used. The purpose of this study was to compare the internal fit of laser-sintered Co-Cr alloy crowns with base metal restorations prepared from another Co-Cr alloy and a Ni-Cr alloy using conventional casting techniques. Internal fit of laser-sintered Co-Cr crowns was compared with the fit of conventionally cast Ni-Cr and Co-Cr alloy crowns. Twelve crown-shaped specimens were prepared on a stainless steel die representing a prepared maxillary right central incisor for each group. Fit of crowns was evaluated using 2 different techniques: (1) weighing the light-body addition silicone that simulated a cement material, and (2) measuring the internal gap width on a die for longitudinally sectioned specimens. One-way ANOVA followed by Tukey multiple comparison test was used for statistical analysis (alpha=.05). Significantly higher mean (SD) light-body silicone weights (Pcrowns. However, no significant difference was found among the 3 alloy groups evaluated for the internal gap width of sectioned crown specimens.

  19. Fracture resistance of zirconia-composite veneered crowns in comparison with zirconia-porcelain crowns.

    OpenAIRE

    Alsadon, O.; Patrick, D.; Johnson, A.; Pollington, S.; Wood, D.

    2017-01-01

    The objectives were to evaluate the fracture resistance and stress concentration in zirconia/composite veneered crowns in comparison to zirconia/porcelain crowns using occlusal fracture resistance and by stress analysis using finite element analysis method. Zirconia substructures were divided into two groups based on the veneering material. A static load was applied occlusally using a ball indenter and the load to fracture was recorded in Newtons (N). The same crown design was used to create ...

  20. Methods for evaluating crown area profiles of forest stands

    Science.gov (United States)

    Dubrasich, Michael E.; Hann, D.W.; Tappeiner, J. C.

    1997-01-01

    Canopy architectures of five structurally complex forest stands and three structurally simple forest stands in southwest Oregon and the Willamette Valley, Oregon, were evaluated and quantified through crown area profiles. Mixed conifer and mixed conifer hardwood stands across a range of sites were sampled for crown widths and heights. Crown width and shape equations were derived and used to quantify the stand crown area at incremental heights above the forest floor. Crown area profiles describe the spatial arrangement of aboveground forest vegetation and the total pore spaces between crowns. Plot by plot profiles were combined to produce vertical and horizontal displays of the stand crown area distribution. In complex stands, the forest space was moderately occupied by crowns from the forest floor up to heights over 30 m, producing uniform distributions of between-crown porosity. The structurally complex stands had between-crown porosity values of 70% to 90% for more than 23 vertical metres of canopy, and they had total between-crown porosities of 86% to 91%. The structurally simple stands had between-crown porosity values of 70% to 90% for less than 8 vertical metres of canopy, and they had total between-crown porosities of 69% to 85%. Variances in crown area indicate that variation in horizontal crown area (within heights) was larger in complex stands than in simple stands, but vertical crown areas (between heights) varied less in complex stands. The study provides a basis for discriminating between canopy architectures and for quantifying the porosity of forest canopies.

  1. 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...

  2. New macrocycles with potent antituberculosis activity accessed by one-pot multicomponent reactions

    NARCIS (Netherlands)

    Kim, D.; Huang, Y.; Wang, K.; Doemling, A.

    Based on modeling studies, we hypothesized that tylosin derivatives without formyl group should rather adopt an erythromycin-like binding mode to the ribosome. Twenty four 16-membered macrocyclic compounds were accessed by multicomponent reactions (Gewald, Ugi) of tylosin and investigated for their

  3. 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...

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

    Indian Academy of Sciences (India)

    Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations. ANURADHA SANKARANa,b, E J PADMA MALARc,∗ and. VENKATAPURAM RAMANUJAM VIJAYARAGHAVANa,∗. aDepartment of Physical Chemistry, ...

  5. Sulfur-Switch Ugi Reaction for Macrocyclic Disulfide-Bridged Peptidomimetics

    NARCIS (Netherlands)

    Vishwanatha, Thimmalapura M; Bergamaschi, Enrico; Dömling, Alexander

    2017-01-01

    A general strategy is introduced for the efficient synthetic access of disulfide linked artificial macrocycles via a Ugi four-component reaction (U4CR) followed by oxidative cyclization. The double-mercapto input is proposed for use in the Ugi reaction, thereby yielding all six topologically

  6. 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).

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Peptide-derived protease inhibitors are an important class of compounds with the potential to treat a wide range of diseases. Herein, we describe the synthesis of a series of triazole- containing macrocyclic protease inhibitors pre-organized into a b-strand conformation and an evaluation...

  8. Macrocyclic ligands for uranium complexation: Progress report, August 15, 1986--January 28, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.

    1989-01-28

    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ion, have been prepared and their ability to complex the uranyl ion 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. The macrocycles studied formed uranyl complexes in solution but no crystalline complexes have been isolated to date. Acyclic ligands containing the same atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex 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 behave 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. 21 refs., 7 figs., 10 tabs.

  9. Fe(III) complex of biuret-amide based macrocyclic ligand as peroxidase enzyme mimic.

    Science.gov (United States)

    Panda, Chakadola; Ghosh, Munmun; Panda, Tamas; Banerjee, Rahul; Sen Gupta, Sayam

    2011-07-28

    An Fe(III) complex of a biuret-amide based macrocyclic ligand that exhibits both excellent reactivity for the activation of H(2)O(2) and high stability, especially at low pH and high ionic strength, is reported.

  10. 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...

  11. 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.

  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. 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

  14. Long-term clinical performance of esthetic primary molar crowns.

    Science.gov (United States)

    Ram, Diana; Fuks, Anna B; Eidelman, Eliecer

    2003-01-01

    The aim of the study was to report the long-term clinical performance of esthetic primary molar crowns and compare them to that of stainless steel crowns (SSC). Twenty crowns (10 conventional and 10 esthetic) placed in 10 children who had participated in a previously reported study, were assessed again after 4 years. The crowns were evaluated clinically and radiographically according to the following parameters: gingival health, marginal extension, crown adequacy, proper occlusion, proximal contact, chipping of the facing (for esthetic crowns only), and cement removal. At the 4 year evaluation, all the esthetic crowns showed chipping of the facing. No difference was found for marginal extension, occlusion, crown adequacy and periodontal health between SSCs and the esthetic crowns. After 4 years, all the esthetic crowns presented chipping of the facing and, consequently, a very poor esthetic appearance.

  15. 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...

  16. 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

  17. Comparison of the fracture strengths of metal-ceramic crowns and three ceromer crowns.

    Science.gov (United States)

    Ku, Chul-Whoi; Park, Sang-Won; Yang, Hong-So

    2002-08-01

    The fracture strength of a number of new ceromer systems for the fabrication of anterior fixed partial dentures is unknown. The purpose of this study was to compare the fracture strengths of metal-ceramic crowns and 3 types of ceromer crowns in a simulated anterior tooth preparation. A resin maxillary central incisor analog was prepared with a 5-degree convergence angle and a 90-degree, 1-mm shoulder. The incisal edge was reduced by 2 mm, and the axiogingival and axioincisal line angles were rounded. A mold of this tooth was made with vinyl polysiloxane impression material. Ten wax patterns were made from the mold and cast in a nickel-chromium alloy for the fabrication of metal dies, from which 10 metal-ceramic crowns were fabricated. Ten crowns for each of 3 ceromer systems (Artglass, Sculpture, and Targis) were fabricated from the same metal die. Each crown group was prepared, polymerized, air-particle abraded, and finished in accordance with the specific manufacturer's instructions. All 4 types of finished crowns were luted to the dies and embedded in polymethyl methacrylate resin blocks. Their fracture resistance was tested in a universal testing machine. The load was directed at the incisolingual line angle, at 130 degrees to the long axis of each specimen, until catastrophic failure occurred. A 7-mm-diameter rod was used to load the artificial crowns, with the center of the rod in contact with the crown surfaces. Analysis of variance and Tukey's multiple comparisons test (Pceromer crowns (1317 vs 602 N, respectively) (Pceromer crowns tested, although significantly lower than the values for metal-ceramic crowns, still exceeded normal occlusal forces.

  18. 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.

  19. 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...

  20. Restoring crown fractures by direct composite layering using transparent strip crowns.

    Science.gov (United States)

    Eden, Ece; Taviloğlu, Engin

    2016-04-01

    Traumatic dental injuries are mostly seen at childhood and adolescence. The most common fracture in permanent anterior teeth is crown fracture. Esthetic and easy rehabilitation of these anterior teeth is possible using layering techniques and direct composite resin restorations. Shape, color and surface texture are the most important factors in restoring crown fractures esthetically. This article illustrates how to perform an esthetic composite resin restoration of crown fractures using strip crowns. The technique suggests using a strip crown as a mold for direct resin composite restoration. This provides a cost-effective treatment with operator friendly approach where most outstanding advantage is the minimum chair-side time with a single visit that is very important for young trauma patients. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  1. 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.

  2. 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

    2017-01-01

    Abstract 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. PMID:28715083

  3. Construction and screening of vast libraries of natural product-like macrocyclic peptides using in vitro display technologies.

    Science.gov (United States)

    Bashiruddin, Nasir K; Suga, Hiroaki

    2015-02-01

    Macrocyclic structure and backbone N-methylation represent characteristic features of peptidic natural products, which play critical roles in their biological activity. Although natural products have been the traditional source of such peptides, recent developments in synthesizing natural product-like macrocyclic peptides using reconstituted translation systems have enabled us to construct vast trillion-member libraries of non-standard macrocyclic peptides. In addition, a method for displaying such libraries on their corresponding mRNA templates allows us to rapidly screen them for potent ligands against various drug targets. This review describes methodologies for the ribosomal synthesis of novel natural product-like macrocyclic peptides and their recent applications in the discovery of bioactive molecules using in vitro display technologies. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

  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. Indications & predisposing factors of crown lengthening surgery

    Directory of Open Access Journals (Sweden)

    Arghavan Amini-Behbahani

    2014-09-01

    Full Text Available Introduction: Since crown lengthening surgery could be accompanied by stress, pain and discomfort, knowledge about its predisposing factors could reduce the demands for such surgery.The aim of this study was to identify the most important indications of crown lengthening surgery in order to present new ideas to clinicians on how to reduce the need for this surgery. Methods: This cross-sectional study was done on 470 patients (aged 12-89 years referred for crown lengthening surgery. The patients' demographic data and their reasons for surgery, the teeth restoration condition and its type, condition of the opposite tooth, type of fractured cusp (posterior teeth, root canal therapy condition and quality, and size of existing intracanal posts were recorded in a data sheet. Data were analyzed by using SPSS software.The chi-square and fisher exact test were used for statistical analysis. The significant difference was p<0.05. Results: The most frequent indication in men and women was dental caries followed by tooth fracture.The second upper premolars and first lower molars needed crown lengthening surgery more often, respectively. Conclusions: Since dental caries and fracture are the most important factors that predispose teeth to crown lengthening surgery, controlling caries with a regular recall sequence can reduce the need for such surgery, especially in the elderly.

  6. 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...

  7. The addition of a second lanthanide ion to increase the luminescence of europium(III) macrocyclic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Bromm, A.J. Jr.; Vallarino, L.M. [Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Chemistry; Leif, R.C. [Newport Instruments, San Diego, CA (United States); Quagliano, J.R. [Los Alamos National Lab., NM (United States)

    1998-12-29

    At present, the microscopic visualization of luminescent labels containing lanthanide(III) ions, primarily europium(III), as light-emitting centers is best performed with time-gated instrumentation, which by virtually eliminating the background fluorescence results in an improved signal to noise ratio. However, the use of the europium(III) macrocycle, Quantum Dye{trademark}, in conjunction with the strong luminescence enhancing effect (cofluorescence) of yttrium(III) or gadolinium(III), can eliminate the need for such specialized instrumentation. In the presence of Gd(III), the luminescence of the Eu(III)-macrocycles can be conveniently observed with conventional fluorescence instrumentation at previously unattainable low levels. The Eu(III) {sup 5}D{sub 0} {r_arrow} {sup 7}F{sub 2} emission of the Eu(III)-macrocycles was observed as an extremely sharp band with a maximum at 619 nm and a clearly resolved characteristic pattern. At very low Eu(III)-macrocycle concentrations, another sharp emission was detected at 614 nm, arising from traces of Eu(III) present in even the purest commercially available gadolinium products. Discrimination of the resolved emissions of the Eu(III)-macrocycle and Eu(III) contaminant should provide a means to further lower the limit of detection of the Eu(III)-macrocycle.

  8. 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

  9. 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.

  10. Re(I) derivatives functionalised with thioether crowns containing the 1,10-phenanthroline subunit as a new class of chemosensors.

    Science.gov (United States)

    Casula, Arianna; Nairi, Valentina; Fernández-Moreira, Vanesa; Laguna, Antonio; Lippolis, Vito; Garau, Alessandra; Gimeno, M Concepción

    2015-11-14

    A series of luminescent fac-[Re(CO)3(L)(NN)](+) complexes, where L is a pyridine or an imidazole and NN is the 1,10-phenanthroline subunit of mixed donor pentadentate thioether crowns have been synthesised and their luminescence properties have been analysed. Then, heterometallic Re(i)/Au(i) complexes, with the Au(i) fragment bonded directly to the imidazole ligand, and heterometallic Re(i)/Ag(i) complexes, with the silver fragment coordinating the S-donor thioether linker of the rings have also been prepared. Analysis of their luminescence properties showed a considerable blue shift of the emission maxima for the Re(i)/Ag(i) derivatives, upon coordination of the silver centre to the S-donor atoms of the aliphatic chain of the macrocyclic units.

  11. Clinical Evaluation and Parental Satisfaction with Pediatric Zirconia Anterior Crowns.

    Science.gov (United States)

    Holsinger, Daniel M; Wells, Martha H; Scarbecz, Mark; Donaldson, Martin

    2016-01-01

    The purpose of this study was to evaluate the clinical success of and parental satisfaction with anterior pediatric zirconia crowns. A retrospective analysis of maxillary anterior pediatric zirconia crowns was performed. Crowns were evaluated for retention, gingival health, color match, contour, marginal integrity, and opposing tooth wear. Parental satisfaction regarding the esthetics of the crowns and parental perception of the impact of treatment on the child's appearance and oral health were evaluated by questionnaire. Fifty-seven crowns were evaluated in 18 children. Eight teeth were lost to exfoliation, three were extracted due to pathology, and two crowns debonded, leaving 44 available for examination. The average crown age at time of examination was 20.8 months. Sixteen crowns (36 percent) displayed gingival inflammation and color mismatch. No recurrent caries or opposing tooth wear was noted. Parents reported high satisfaction with the color, size, and shape of the crowns. The majority of parents reported that crowns improved the appearance and oral health of their child (78 percent and 83 percent, respectively). Eight-nine percent of parents reported that they would highly recommend these crowns. Zirconia crowns are clinically acceptable restorations in the primary maxillary anterior dentition. Parental satisfaction with zirconia crowns is high.

  12. Polymers containing nickel(II) complexes of Goedken's macrocycle: optimized synthesis and electrochemical characterization.

    Science.gov (United States)

    Paquette, Joseph A; Sauvé, Ethan R; Gilroy, Joe B

    2015-04-01

    The synthesis and characterization of a new class of nickel-containing polymers is described. The optimized copolymerization of alkyne-bearing nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and brominated 9,9-dihexylfluorene produced polymers with potential application as functional redox-active materials. The title polymers exhibit electrochemically reversible, ligand-centered oxidation events at 0.24 and 0.73 V versus the ferrocene/ferrocenium redox couple. They also display exceptional thermal stability and interesting absorption properties due to the presence of the macrocyclic nickel(II) complexes and π-conjugated units incorporated in their backbones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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...... on these findings, the Panel is of the opinion that there are no safety concerns for the MLs at reported levels of use and exposure as fragrance ingredients...

  14. Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers

    Science.gov (United States)

    Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola

    2016-05-01

    An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

  15. 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.

  16. 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.

  17. Synthesis, antimicrobial, antioxidant and molecular docking studies of thiophene based macrocyclic Schiff base complexes

    Science.gov (United States)

    Rathi, Parveen; Singh, D. P.

    2015-11-01

    The macrocyclic complexes of pharmaceutical importance with trivalent transition metals have been synthesized by [1 + 1] condensation of succinyldihydrazide and thiophenedicarboxaldehyde, via template method, resulting in the formation of the complex [MLX] X2; where L is (C10H10N4O2S), a macrocyclic ligand, M = Cr (III) and Fe (III) and X = Cl-, CH3COO- or NO3- . These complexes have been characterized with the help of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, ultraviolet, infrared, far infrared, electron spin resonance, mass spectral studies and powder x-ray diffraction analysis. On the basis of all these studies, mononuclear complexes having 1:2 electrolytic nature with a five coordinated square pyramidal geometry have been proposed. Powder diffraction XRD indicates the presence of triclinic crystal system with p bravais lattice for the representative complex. All the metal complexes have also been explored for their in vitro antimicrobial and antioxidant activities.

  18. 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.

  19. 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).

  20. Synthesis and Photophysical Properties of Biphenyl and Terphenyl Arylene?Ethynylene Macrocycles

    OpenAIRE

    Korich, Andrew L.; McBee, Ian A.; Bennion, Jonathan C.; Gifford, Jenna I.; Hughes, Thomas S.

    2014-01-01

    A series of single-walled carbon nanotube precursors, C 3h -symmetric cyclotri(ethynylene)(biphenyl-2,4?-diyl) and cyclotri(ethynylene)(p-terphenyl-2,4?-diyl), have been prepared by a linear stepwise oligomerization?cyclization route and by statistical intermolecular cyclooligomerization. In addition to producing these members of a novel class of arylene ethynylene macrocycles, 1 and 2, the latter statistical process produces the smaller cyclic dimer, cyclodi(ethynylene)(p-terphenyl-2,4?-diyl...

  1. 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....... Sceliphrolactam displays antifungal activity against amphotericin B-resistant Candida albicans (MIC = 4 µg/mL, 8.3 µM)....

  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. Biomechanical Assessment of Strength and Jumping Ability in Male Volleyball Players During the Annual Training Macrocycle

    Directory of Open Access Journals (Sweden)

    Czaplicki Adam

    2017-12-01

    Full Text Available Introduction. The aim of the study was to determine the changes in the peak torque of the knee extensors and flexors of the dominant lower limb, the shoulder internal and external rotators of the dominant upper limb, and the shoulder extensors and flexors of the dominant upper limb as well as the changes in jump height in volleyball players during the annual training macrocycle.

  4. Confined Synthesis of Organometallic Chains and Macrocycles by Cu-O Surface Templating.

    Science.gov (United States)

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

    2016-03-22

    The bottom-up construction of low-dimensional macromolecular nanostructures directly on a surface is a promising approach for future application in molecular electronics and integrated circuit production. However, challenges still remain in controlling the formation of these nanostructures with predetermined patterns (such as linear or cyclic) or dimensions (such as the length of one-dimensional (1D) chains). Here, we demonstrate that a high degree of structural control can be achieved by employing a Cu(110)-(2×1)O nanotemplate for the confined synthesis of organometallic chains and macrocycles. This template contains ordered arrays of alternating stripes of Cu-O chains and bare Cu, the widths of which are controllable. Using scanning tunneling microscopy and low-energy electron diffraction, we show that well-defined, ordered 1D zigzag organometallic oligomeric chains with uniform lengths can be fabricated on the Cu stripes (width >5.6 nm) of the Cu(110)-(2×1)O surface. In addition, the lengths of the meta-terphenyl (MTP)-based chains can be adjusted by controlling the widths of the Cu stripes within a certain range. When reducing the widths of Cu stripes to a range of 2.6 to 5.6 nm, organometallic macrocycles including tetramer (MTP-Cu)4, hexamer (MTP-Cu)6, and octamer (MTP-Cu)8 species are formed due to the spatial confinement effect and attraction to the Cu-O chains. An overview of all formed organometallic macrocycles on the Cu stripes with different widths reveals that the origin of the formation of these macrocycles is the cis-configured organometallic dimer (MTP)2Cu3, which was observed on the extremely narrow Cu stripe with a width of 1.5 nm.

  5. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Science.gov (United States)

    2010-04-01

    ... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3770 Temporary crown and bridge resin. (a... polymethylmethacrylate, intended to make a temporary prosthesis, such as a crown or bridge, for use until a permanent...

  6. Relative Clinical Success of Bis-Acryl Composite Provisional Crowns.

    Science.gov (United States)

    Kozmacs, Carla; Baumann, Vanessa; Bunz, Oskar; Piwowarczyk, Andree

    2018-01-01

    The high demands on the clinical performance of a single-tooth provisional restoration necessitate that said performance be examined. The authors evaluated 24 teeth evaluated. Two test groups received bis-acrylic composite for provisional crowns (n = 12) and a single-unit, self-supporting, malleable, light-curing composite crown (n = 12). Final crowns (n = 24) served as paired controls. Evaluation of clinical success was measured using previously selected subcategories of FDI criteria. Statistical analysis was performed using McNemar's Test (α = 0.05). The null hypothesis of no improvement of the definitive crown relative to the provisionals was rejected at the 5% significance level (McNemar's P value provisional crowns, 75% received a clinically insufficient valuation, while only 8% of the definitive crowns did. The authors concluded that, independent of the manufacturing process, a bis-acrylic composite provisional crown cannot serve as a replacement for a conventionally manufactured definitive crown.

  7. 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.

  8. 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.

  9. Insulin mimetic effects of macrocyclic binuclear oxovanadium complexes on streptozotocin-induced experimental diabetes in rats.

    Science.gov (United States)

    Ramachandran, B; Kandaswamy, M; Narayanan, V; Subramanian, S

    2003-11-01

    The vanadium complexes so far tested for their insulin mimetic effects are either mono- or binuclear and contain only acyclic ligands. The leaching or hydrolysis of vanadyl ions from these complexes is much easier, and hence they elicit side effects. In the present study, a new binuclear macrocyclic oxovanadium complex was synthesized, and its efficacy was studied on streptozotocin (STZ)-induced diabetic rats over a period of 30 days. The insulin mimetic effect of the complex was tested on the blood sugar level in the STZ-diabetic rats and on the activities of the carbohydrate-metabolizing enzymes present in the liver. Administration of vanadium complex to STZ-induced diabetic rats decreased blood glucose levels from hyperglycaemic to normoglycaemic when compared to diabetic rats. The activity of carbohydrate-metabolizing enzymes such as hexokinase, glucose-6-phosphate dehydrogenase, glycogen synthase and glycogen content were increased to near normal in vanadium complex-administered diabetic rats. The biochemical studies such as assay of blood urea and glutamate oxaloacetate transaminases revealed that the complex is not toxic to the system. The nontoxic nature of this complex may be due to the presence of the vanadyl ions in an intact macrocyclic form. Further, the vanadyl ions present in the macrocyclic binuclear oxovanadium complex are very close to each other, and this may enhance the insulin mimetic activity by synergic effect.

  10. 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.

  11. 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

  12. 21 CFR 872.3330 - Preformed crown.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Preformed crown. 872.3330 Section 872.3330 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL... device also may be intended for use as a functional restoration for a badly decayed deciduous (baby...

  13. Internal adaptation of cast titanium crowns

    Directory of Open Access Journals (Sweden)

    Sicknan Soares da Rocha

    2007-08-01

    Full Text Available As the adaptation of titanium crowns obtained by Rematitan Plus investment, specific for titanium, is not recognized to be suitable, this study evaluated the effect of the concentration of the specific liquid and the temperature of the mold of investments on the internal misfit of crowns cast on commercially pure titanium. Individual dies of epoxy resin were obtained, representing teeth prepared for full-crown restoration with a 6-degree axial surface convergence angle and shoulder (1.0 mm. For the waxing of each crown, a ring-shaped stainless steel matrix (8.0mm internal diameter; 7.5 mm height was adapted above the individual dies of epoxy resin. The Rematian Plus investment was mixed according to the manufacturer's instructions using two different concentrations of the specific liquid: 100%, 75%. Casting was performed in a Discovery Plasma Ar-arc vacuum-pressure casting machine with molds at temperatures of 430ºC, 515ºC and 600ºC. The crowns were cleaned individually in a solution (1% HF + 13% HNO3 for 10 min using a ultrasonic cleaner, with no internal adaptations, and luted with zinc phosphate cement under a 5 kg static load. The crown and die assemblies were embedded in resin and sectioned longitudinally. The area occupied by cement was observed using stereoscopic lens (10X and measured by the Leica Qwin image analysis system (mm². The data for each experimental condition (n=8 were analyzed by Kruskal-Wallis non-parametric test (á=0.05. The results showed that liquid dilution and the increase in mold temperature did not significantly influence the levels of internal fit of the cast titanium crowns. The lowest means (±SD of internal misfit were obtained for the 430ºC/100%: (7.25 mm² ±1.59 and 600ºC/100% (8.8 mm² ±2.25 groups, which presented statistically similar levels of internal misfit.

  14. 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

  15. Two-body wear comparison of zirconia crown, gold crown, and enamel against zirconia.

    Science.gov (United States)

    Kwon, Min-Seok; Oh, Sang-Yeob; Cho, Sung-Am

    2015-07-01

    Full zirconia crowns have recently been used for dental restorations because of their mechanical properties. However, there is little information about their wear characteristics against enamel, gold, and full zirconia crowns. The purpose of this study was to compare the wear rate of enamel, gold crowns, and zirconia crowns against zirconia blocks using an in vitro wear test. Upper specimens were divided into three groups: 10 enamels (group 1), 10 gold crowns (group 2, Type III gold), and 10 zirconia crowns (group 3, Prettau(®)Zirkon 9H, Zirkonzahn, Italy). Each of these specimens was wear tested against a zirconia block (40×30×3mm(3)) as a lower specimen (30 total zirconia blocks). Each specimen of the groups was abraded against the zirconia block for 600 cycles at 1Hz with 15mm front-to-back movement on an abrading machine. Moreover, the load applied during the abrading test was 50N, and the test was performed in a normal saline emulsion for 10min. Three-dimensional images were taken before and after the test, and the statistical analysis was performed using the Krushal-Wallis test and Mann-Whitney test (p=0.05). The mean volume loss of group 1 was 0.47mm(3), while that of group 2 and group 3 was 0.01mm(3). The wear volume loss of enamels against zirconia was higher than that of gold and zirconia crowns. Moreover, according to this result, zirconia crowns are not recommended for heavy bruxers. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. 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

  17. 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...

  18. 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...

  19. Crown dilacerations - Two case reports | Rao | Nigerian Dental Journal

    African Journals Online (AJOL)

    Crown dilaceration is a relatively abnormal clinical finding when compared to root dilacerations. The incidence of crown dilacerations is stated to be as low as 3%. This report presents two cases of crown dilacerations in two different locations. A brief review of the literature pertinent to the condition, and the clinical and ...

  20. Proton-Ionizable Crown Ethers. A Short Review

    Science.gov (United States)

    1989-05-30

    Triazole’Subcyclic Unit 14. Proton-Ionizable Crown Ethers Containing Sulfonamide Groups 15. Miscellaneous Proton-Ionizable Crown Ethers 1. INTRODUCTION. ""Since...the diaza dinitrile crown. Subsequent hydrolysis produced the diacid 33 (Procedure E). 27 Monoaza-crowns 35-38 (Figure V, Table 5) were obtained by the...followed by hydrolysis of the cetidi to f the acid.3o Complextion by th~eam crownsJ hasJ boon extensively castudieon and transportat es of thos ecaions have

  1. 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.

  2. 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.

  3. Fracture resistance of monolithic zirconia molar crowns with reduced thickness.

    Science.gov (United States)

    Nakamura, Keisuke; Harada, Akio; Inagaki, Ryoichi; Kanno, Taro; Niwano, Yoshimi; Milleding, Percy; Örtengren, Ulf

    2015-01-01

    The purpose of the present study was to analyze the relationship between fracture load of monolithic zirconia crowns and axial/occlusal thickness and to evaluate the fracture resistance of monolithic zirconia crowns with reduced thickness in comparison with that of monolithic lithium disilicate crowns with regular thickness. Monolithic zirconia crowns (Lava Plus Zirconia, 3M/ESPE) with specified axial/occlusal thicknesses and lithium disilicate crowns (IPS e.max press, Ivoclar/Vivadent) with regular thickness were fabricated using a dental CAD/CAM system and a press technique, respectively. The crowns cemented onto dies were loaded until fracture. Based on measurements of the crown thickness made by micro-CT and the fracture load, multiple regression analysis was performed. It was revealed that the occlusal thickness significantly affected the fracture load (p zirconia crowns, the fracture load of the zirconia crowns with the occlusal thickness of 0.5 mm (5558 ± 522 N) was significantly higher than that of lithium disilicate crowns with an occlusal thickness of 1.5 mm (3147 ± 409 N). Within the limitations of the present study, it is suggested that monolithic zirconia crown with chamfer width of 0.5 mm and occlusal thickness of 0.5 mm can be used in the molar region in terms of fracture resistance.

  4. Cerec anterior crowns: restorative options with monolithic ceramic materials.

    Science.gov (United States)

    Reich, Sven; Fiedlar, Kurt

    2013-01-01

    The aim of this article is to discuss the different types of monolithic ceramic crowns that can be placed on anterior teeth with existing shoulder preparations. Anterior crowns were indicated for the teeth 12 to 22 in the present case. The patient, a 65-year-old male, had received all-ceramic crowns 20 years earlier, which had started to develop cracks and palatal fractures over the last few years. The patient's teeth were prepared and four sets of crowns were fabricated using different monolithic ceramic materials: IPS e.max CAD, Cerec Blocs C In, VITABLOCS Real Life, and ENAMIC. Both shade characterization and crystallization firing were performed on the monolithic lithium disilicate glass ceramic crowns. The silicate ceramic crowns received glaze firing alone. The crowns made of hybrid ceramic (ENAMIC) were treated with a polymer sealant.

  5. Crown structure of Picea omorika trees in the plantation

    Directory of Open Access Journals (Sweden)

    Krstić M.

    2012-01-01

    Full Text Available The study was carried out in Serbian spruce (Picea omorika Panč/Purkynĕ plantations in the western Serbia. The paper presents results of the analysis of crown development. The following elements were analyzed: total tree height, height of the crown base, absolute and relative crown length, maximal crown diameter, coefficient of crown spreading and degree of crown girth. We discuss approaches to the modeling of tree crown growth and development, growing under favorable environmental and stand conditions, without anomalies in development. In order to establish the relationship between analyzed factors, regression analyses were applied. Data fitting was by the analytic method, by the implementation of Prodan’s functions of growth, linear and parabolic function. Received models can be used for the simulation of various growth and developing processes in forest.

  6. TRANSFORMATIONS OF BENZO-15-CROWN-5, [3.3]DIBENZO-18-CROWN-6 AND [4.4]DIBENZO-24-CROWN-8 IN AQUEOUS SOLUTIONS OF NITRIC ACID

    Directory of Open Access Journals (Sweden)

    S. M. Pluzhnik-Gladyr

    2015-02-01

    Full Text Available Peculiarities of benzo-15-crown-5 (I, [3.3]dibenzo-18-crown-6 (II, and [4.4]diben zo-24-crown-8 (III nitration by the dilute nitric acid and the mixture HCl-HNO3(4:1, «aqua regia» at room temperature are discussed. It was revealed that the «reactivity» of studied crown ethers (symbatically/antisymbatic to their hydrophili ci ty/lipophilicity is variated as follows: I>> III> II.

  7. 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...

  8. Antagonist wear by polished zirconia crowns.

    Science.gov (United States)

    Hartkamp, Oliver; Lohbauer, Ulrich; Reich, Sven

    The aim of this in vivo study was to measure antagonist wear caused by polished monolithic posterior zirconia crowns over a 24-month period using the intraoral digital impression (IDI) technique. Thirteen zirconia crowns were placed in nine patients. The crowns and adjacent teeth were captured using an intraoral scanner (Lava C.O.S.). The corresponding antagonist teeth and the respective neighboring teeth were also scanned. Scanning was performed immediately after the restoration (baseline) as well as 12 and 24 months after crown placement. Geomagic Qualify software was used to superimpose the follow-up data sets onto the corresponding baseline data set, identify wear sites, and measure maximum vertical height loss in each individual wear site. Overall antagonist wear was then determined as the mean of wear rates measured in all of the individual antagonist units. In addition, wear rates in enamel and ceramic antagonists were analyzed as part of the scope of this study. The maximum mean wear with standard deviation (SD) in the overall sample with a total of nine patients, 13 antagonist units, and 98 evaluable wear sites was 86 ± 23 µm at 12 months, and 103 ± 39 µm at 24 months. The maximum mean wear in the enamel antagonist subgroup was 87 ± 41 µm at 12 months, and 115 ± 71 µm at 24 months; and in the ceramic antagonist subgroup 107 ± 22 µm at 12 months, and 120 ± 27 µm at 24 months. The wear rates determined in this study are comparable to those of existing studies. The IDI technique of wear analysis can be carried out in a practical manner and produces useful results.

  9. Rigid Organization of Fluorescence-Active Ligands by Artificial Macrocyclic Receptor to Achieve the Thioflavin T-Amyloid Fibril Level Association.

    Science.gov (United States)

    Zhang, Ying-Ming; Zhang, Xu-Jie; Xu, Xiufang; Fu, Xiao-Ning; Hou, Hong-Biao; Liu, Yu

    2016-04-28

    The push-pull molecules with an intramolecular charge transfer from donor to acceptor sides upon excitation exhibit a wide variety of biological and electronic activities, as exemplified by the in vivo fluorescence imaging probes for amyloid fibrils in the diagnosis and treatment of amyloid diseases. Interestingly, the structurally much simpler bis(4,8-disulfonato-1,5-naphtho)-32-crown-8 (DNC), in keen contrast to the conventional macrocyclic receptors, was found to dramatically enhance the fluorescence of twisted intramolecular charge-transfer molecules possessing various benzothiazolium and stilbazolium fluorophores upon complexation. Spectroscopic and microcalorimetric titrations jointly demonstrated the complex structures and the interactions that promote the extremely strong complexation, revealing that the binding affinity in these artificial host-guest pairs could reach up to a nearly 10(7) M(-1) order of magnitude in water, and the sandwich-type complexation is driven by electrostatic, hydrophobic, π-stacking, and hydrogen-bonding interactions. Quantum chemical calculations on free molecules and their DNC-bound species in both the ground and excited states elucidated that the encapsulation by DNC could greatly deter the central single and double chemical bonds from free intramolecular rotation in the singlet excited state, thus leading to the unique and unprecedented fluorescence enhancement upon sandwich-type complexation. This complexation-induced structural reorganization mechanism may also apply to the binding of other small-molecule ligands by functional receptors and contribute to the molecular-level understanding of the receptor-ligand interactions in many biology-related systems.

  10. 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

  11. 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.

  12. An Investigation Into the Integrity of Fit of Provisional Crowns Using Current Proprietary Temporary Crown Materials.

    Science.gov (United States)

    Taylor, Philip D; Georgakis, Georgios; Niggli, Jason

    2016-06-01

    Three methods of direct provisional crown construction were investigated for accuracy of marginal fit. A modified proprietary crown coping was compared to Bis GMA and isobutyl methacrylate resin provisional crowns with margins modified by using a flowable composite and 'bead on' isobutyl methacrylate respectively. Measurement was at 50x magnification at seven sites over the fit surface. Data was analyzed using SPSS version 13.0.1 and measurement compared using the Mann Whitney test set at a significance level of 0.05. Reliability was checked using the Bland Altman test. Statistical significant differences were found between the three groups. The order of best fit was Bis-GMA and flowable composite > isobutyl methacrylate with 'bead on' margins > Bis-GMA modified implant temporary coping. The clinical significance is that the Bis GMA and flowable composite combination can be used with equal confidence to traditional methods of temporarisation.

  13. Synthesis and photoisomerization study of new aza-crown macrocyclic tweezer tethered through an azobenzene linker: The first report on supramolecular interaction of azobenzene moiety with C60

    Science.gov (United States)

    Ghanbari, Bahram; Mahdavian, Mahsa; García-Deibe, A. M.

    2017-09-01

    In the present communication, three bimacrocyclic tweezers linked through azobenzene moiety, Ln (n = 1-3) were synthesized in a multistep route and characterized by x-ray crystallography, IR, 1H and 13C NMR, UV-vis spectroscopy as well as CHN microanalysis. UV-visible spectroscopy established that the irradiation of L1 and L3 with UV light promoted the trans to cis isomerization. Irradiating the reaction mixtures with Hg lamp, significant supramolecular interactions between L1 and L3 with C60 were also found in terms of the association constants calculated by UV-visible spectroscopy, denoting on more pronounced interaction with C60 that in the absence of UV light. The molecular structures of L1-L3 calculated by using DFT method suggested a novel unprecedented interaction between the HOMO's of azobenzene moiety on the tweezer instead of the aromatic groups with C60.

  14. 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.

  15. 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.

  16. 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.

  17. Crystal Structures, Properties and Reactivity of Selected Macrocyclic and Chelate Complexes of Ni(II)

    OpenAIRE

    Churchard, Andrew James

    2012-01-01

    In this dissertation we describe the structure, properties and decomposition reactions of a series of Ni(II) coordination complexes formed from reaction of the appropriate macrocyclic or chelating ligand with a simple nickel salt. The ligands used were 12aneS4 (1,4,7,10-tetrathiacyclododecane), 14aneS4 (1,4,8,11-tetrathiacyclotetradecane), cyclam (1,4,8,11-tetraazacyclotetradecane), dppe (1,2- (diphenylphosphino)ethane), and PP3 (tris-(2-(diphenylphosphino)ethyl)phosphine). The wo...

  18. 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.

  19. Potent toxic macrocyclic trichothecenes from the marine-derived fungus Myrothecium verrucaria Hmp-F73.

    Science.gov (United States)

    Zhao, Li; Liu, Li; Wang, Nan; Wang, Shu-Jin; Hu, Jing-Chun; Gao, Jin-Ming

    2011-12-01

    Activity-guided fractionation of a methanol extract from the culture broth of Myrothecium verrucaria Hmp-F73, a fungus associated with the sponge Hymeniacidon perleve, afforded six macrocyclic trichothecenes, verrucarin J (1), 8-hydroxyverrucarin J (2), verrucarin A (3), 8-acetoxyroridin H (4), isororidin E (5), and roridin E (6), along with trichoverrin B (7). All seven metabolites displayed potent toxicity to the brine shrimp (Artemia salina). In addition, compounds 2, 3, and 6 showed weak phytotoxic activities against lettuce seeds. A preliminary structure-activity relationship of the metabolites is also discussed.

  20. 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.

  1. 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.

  2. Retention behavior of double-crown attachments with zirconia primary and secondary crowns.

    Science.gov (United States)

    Schwindling, Franz Sebastian; Stober, Thomas; Rustemeier, Rainer; Schmitter, Marc; Rues, Stefan

    2016-05-01

    To investigate whether adequate retention of zirconia conical crown (CC) attachments can be achieved, and to investigate their long-term retention. Sixteen individual zirconia primary crowns were produced with convergence angles of 1° or 2° (eight of each). After determination of the convergence angles of the primary crowns, monolithic zirconia secondary crowns were manufactured. To evaluate the retention behavior of all-zirconia CC, the crowns were fitted with forces from F=12.5-100 N. Force magnitudes during the loosening process (L) were then measured. L/F ratios were recorded and the coefficient of friction (μ0) was calculated. Long-term retention was tested with up to 50,000 cycles of denture integration at a speed of 30 mms(-1) and a fitting force magnitude of 53 N. Even when primary crowns were manufactured with the utmost care, the real convergence angles were greater than the nominal angles of the standardized burs (1° and 2°) by 0.28° (SD 0.11°). Without mechanical aging, mean L/F was 0.632 (SD 0.038) for 1° samples and 0.526 (SD 0.022) for 2° samples, indicative of high retentive forces of up to 63.2% of the fitting forces. When all the test results were used, best-fitting curves gave μ0=0.117 for new samples and μ0=0.126 for samples after 50,000 integration cycles. When the correct milling and sintering parameters are chosen, the retention behavior of zirconia CCs is adequate and stable. This innovative type of attachment is appealing because of the beneficial properties of zirconia and the efficient CAD/CAM-based manufacture. Copyright © 2016 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  3. 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.

  4. [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.

  5. Fracture resistance of implant- supported monolithic crowns cemented to zirconia hybrid-abutments: zirconia-based crowns vs. lithium disilicate crowns.

    Science.gov (United States)

    Elshiyab, Shareen H; Nawafleh, Noor; Öchsner, Andreas; George, Roy

    2018-02-01

    The aim of this in vitro study was to investigate the fracture resistance under chewing simulation of implant-supported posterior restorations (crowns cemented to hybrid-abutments) made of different all-ceramic materials. Monolithic zirconia (MZr) and monolithic lithium disilicate (MLD) crowns for mandibular first molar were fabricated using computer-aided design/computer-aided manufacturing technology and then cemented to zirconia hybrid-abutments (Ti-based). Each group was divided into two subgroups (n=10): (A) control group, crowns were subjected to single load to fracture; (B) test group, crowns underwent chewing simulation using multiple loads for 1.2 million cycles at 1.2 Hz with simultaneous thermocycling between 5℃ and 55℃. Data was statistically analyzed with one-way ANOVA and a Post-Hoc test. All tested crowns survived chewing simulation resulting in 100% survival rate. However, wear facets were observed on all the crowns at the occlusal contact point. Fracture load of monolithic lithium disilicate crowns was statistically significantly lower than that of monolithic zirconia crowns. Also, fracture load was significantly reduced in both of the all-ceramic materials after exposure to chewing simulation and thermocycling. Crowns of all test groups exhibited cohesive fracture within the monolithic crown structure only, and no abutment fractures or screw loosening were observed. When supported by implants, monolithic zirconia restorations cemented to hybrid abutments withstand masticatory forces. Also, fatigue loading accompanied by simultaneous thermocycling significantly reduces the strength of both of the all-ceramic materials. Moreover, further research is needed to define potentials, limits, and long-term serviceability of the materials and hybrid abutments.

  6. 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.

  7. 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

  8. Zirconia crowns - the new standard for single-visit dentistry?

    Science.gov (United States)

    Wiedhahn, Klaus; Fritzsche, Günter; Wiedhahn, Claudine; Schenk, Olaf

    2016-01-01

    Zirconia crowns combine the advantages of metal restorations, such as minimally invasive tooth preparation and ease of cementation, with those of full ceramic crowns, such as low thermal conductivity and tooth color. With the introduction of a high-speed sintering procedure, it is possible to produce and cement zirconia crowns and small monolithic bridges in a Cerec Single Visit procedure. This new procedure is compared to established chairside methods.

  9. Fracture resistance of monolithic zirconia molar crowns with reduced thickness

    OpenAIRE

    Nakamura, Keisuke; Harada, A.; Inagaki, R.; Kanno, Taro; Niwano, Y.; Milleding, Percy; Ørtengren, Ulf Thore

    2015-01-01

    This is the accepted manuscript version. Published version is available at Acta Odontologica Scandinavica Objectives. The purpose of the present study was to analyze the relationship between fracture load of monolithic zirconia crowns and axial/occlusal thickness, and to evaluate the fracture resistance of monolithic zirconia crowns with reduced thickness in comparison with that of monolithic lithium disilicate crowns with regular thickness. Materials and methods. Monolithic zi...

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

    Science.gov (United States)

    Shembish, Fatma A; Tong, Hui; Kaizer, Marina; Janal, Malvin N; Thompson, Van P; Opdam, Niek J; Zhang, Yu

    2016-04-01

    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. Fully anatomically shaped monolithic resin composite molar crowns (Lava Ultimate, n=24) and leucite reinforced glass-ceramic crowns (IPS Empress CAD, n=24) were fabricated using CAD/CAM systems. Crowns were cemented on aged dentin-like resin composite tooth replicas (Filtek Z100) with resin-based cements (RelyX Ultimate for Lava Ultimate or Multilink Automix for IPS Empress). Three step-stress profiles (aggressive, moderate and mild) were employed for the accelerated sliding-contact mouth-motion fatigue test. Twenty one crowns from each group were randomly distributed among these three profiles (1:2:4). Failure was designated as chip-off or bulk fracture. Optical and electron microscopes were used to examine the occlusal surface and subsurface damages, as well as the material microstructures. The resin composite crowns showed only minor occlusal damage during mouth-motion step-stress fatigue loading up to 1700N. Cross-sectional views revealed contact-induced cone cracks in all specimens, and flexural radial cracks in 2 crowns. Both cone and radial cracks were relatively small compared to the crown thickness. Extending these cracks to the threshold for catastrophic failure would require much higher indentation loads or more loading cycles. In contrast, all of the glass-ceramic crowns fractured, starting at loads of approximately 450N. Monolithic CAD/CAM resin composite crowns endure, with only superficial damage, fatigue loads 3-4 times higher than those causing catastrophic failure in glass-ceramic CAD crowns. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  11. Clinically relevant fracture testing of all-ceramic crowns.

    Science.gov (United States)

    Øilo, Marit; Kvam, Ketil; Tibballs, John E; Gjerdet, Nils Roar

    2013-08-01

    Fracture strength measured in vitro indicates that most all-ceramic crowns should be able to withstand mastication forces. Nevertheless, fractures are one of the major clinical problems with all-ceramic restorations. Furthermore, the fracture mode of all-ceramic crowns observed in clinical use differs from that found in conventional fracture strength tests. The aim of the present study was to develop and investigate a method that simulates clinical fracture behavior in vitro. 30 crowns with alumina cores were made to fit a cylindrical model with a molar-like preparation design. These crowns were randomly allocated to 3 tests groups (n=10). The crowns in group 1 were cemented to abutment models of epoxy and subsequently fractured by occlusal loading without contact damage. The crowns in group 2 were fractured by cementation with expanding cement. The crowns in group 3 were cemented on an abutment model of epoxy split almost in two and fractured by increasing the diameter of the model in the bucco-lingual direction. The fractured crowns were analyzed by fractographic methods and compared to a reference group of 10 crowns fractured in clinical use. The fracture modes of all the in vitro crowns were similar to clinical fracture modes. The fracture modes in group 1 were most closely matched to the clinical fractures. These crowns also fractured at clinically relevant loads. Laboratory tests that induce a distortion of the abutment model during occlusal loading without occlusal contact damage can simulate clinical fractures of all-ceramic crowns. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  12. Fatigue Resistance of CAD/CAM Resin Composite Molar Crowns

    Science.gov (United States)

    Shembish, Fatma A.; Tong, Hui; Kaizer, Marina; Janal, Malvin N.; Thompson, Van P.; Opdam, Niek J.; Zhang, Yu

    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 Ultimate, n = 24) and leucite reinforced glass-ceramic crowns (IPS Empress CAD, n = 24) were fabricated using CAD/CAM systems. Crowns were cemented on aged dentin-like resin composite tooth replicas (Filtek Z100) with resin-based cements (RelyX Ultimate for Lava Ultimate or Multilink Automix for IPS Empress). Three step-stress profiles (aggressive, moderate and mild) were employed for the accelerated sliding-contact mouth-motion fatigue test. Twenty one crowns from each group were randomly distributed among these three profiles (1:2:4). Failure was designated as chip-off or bulk fracture. Optical and electronic microscopes were used to examine the occlusal surface and subsurface damages, as well as the material microstructures. Results The resin composite crowns showed only minor occlusal damage during mouth-motion step-stress fatigue loading up to 1700 N. Cross-sectional views revealed contact-induced cone cracks in all specimens, and flexural radial cracks in 2 crowns. Both cone and radial cracks were relatively small compared to the crown thickness. Extending these cracks to the threshold for catastrophic failure would require much higher indentation loads or more loading cycles. In contrast, all of the glass-ceramic crowns fractured, starting at loads of approximately 450 N. Significance Monolithic CAD/CAM resin composite crowns endure, with only superficial damage, fatigue loads 3 – 4 times higher than those causing catastrophic failure in glass-ceramic CAD crowns. PMID:26777092

  13. Pediatric Preformed Metal Crowns - An Update

    Directory of Open Access Journals (Sweden)

    Sangameshwar Sajjanshetty

    2013-01-01

    Full Text Available Stainless Steel crowns (SSC were introduced in 1947 by the Rocky Mountain Company and popularized by Humphrey in 1950. Prefabricated SSC can be adapted to individual primary teeth and cemented in place to provide a definitive restoration. The SSC is extremely durable, relatively inexpensive, subject to minimal technique sensitivity during placement, and offers the advantage of full coronal coverage. SSC are often used to restore primary and permanent teeth in children and adolescents where intracoronal restorations would otherwise fail. This article brings the update of this definitive restoration.

  14. 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.

  15. Combined molecular and periodic DFT analysis of the adsorption of co macrocycles on graphene.

    Science.gov (United States)

    Calborean, Adrian; Morari, Cristian; Maldivi, Pascale

    2018-01-15

    The molecular doping of graphene with π-stacked conjugated molecules has been widely studied during the last 10 years, both experimentally or using first-principle calculations, mainly with strongly acceptor or donor molecules. Macrocyclic metal complexes have been far less studied and their behavior on graphene is less clear-cut. The present density functional theory study of cobalt porphyrin and phthalocyanine adsorbed on monolayer or bilayer graphene allows to compare the outcomes of two models, either a finite-sized flake of graphene or an infinite 2D material using periodic calculations. The electronic structures yielded by both models are compared, with a focus on the density of states around the Fermi level. Apart from the crucial choice of calculation conditions, this investigation also shows that unlike strongly donating or accepting organic dopants, these macrocycles do not induce a significant doping of the graphene sheet and that a finite size model of graphene flake may be confidently used for most modeling purposes. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  16. 14-Methylpentadecano-15-lactone (muscolide): a new macrocyclic lactone from the oil of Angelica archangelica L.

    Science.gov (United States)

    Lopes, Daíse; Strobl, Herbert; Kolodziejczyk, Paul

    2004-12-01

    The chemical composition of seed and root oils from Angelica archangelica L. was investigated. Analyses were performed by GC/MS and GC using two columns of different polarities (polyethylene glycol (DB-Wax) and 5% phenyl/95% polydimethylsiloxane (HP-5)), for the separation of several co-eluting components. A total of 58 compounds were identified, accounting for 96.3% (seed) and 93.5% (root) of the oils, respectively. A high content of beta-phellandrene (74.7%) was found in Angelica seed oil. Root oil contained a larger amount of macrocyclic lactones (1.3%) in comparison to the seed oil (0.4%). Different harvest dates produced only slight changes in the root-oil composition. In root oil harvested in summer, the beta-phellandrene content increased by ca. 36%, but no significant changes in the relative compositions of other components were observed. Fresh root oils were collected in five fractions (constant time intervals) during steam distillation (see Table). The highest-boiling fraction contained 9.3% of macrocyclic lactones such as tridecano-13-lactone (5.0%), 12-methyltridecano-13-lactone (0.4%), tetradecano-14-lactone (0.1%), pentadecano-15-lactone (3.5%), 14-methylpentadecano-15-lactone (1; trace), hexadecano-16-lactone (trace), and heptadecano-17-lactone (0.2%). This is the first report of the occurrence of 14-methylpentadecano-15-lactone (muscolide; 1) in a natural product.

  17. Response of Critical Speed to Different Macrocycle Phases during Linear Periodization on Young Swimmers

    Directory of Open Access Journals (Sweden)

    João Bartholomeu NETO

    2016-03-01

    Full Text Available Sport training programs to young swimmers have to aggregate different physical stimulus to collaborate with overall physical development, which can lead to reach best results in competitions. Linear periodization seems to be a powerful tool that allow the organization of these stimulus. However, this model has been not studied. Regarding physical capacities, aerobic fitness is inversely related with fatigue and exercise performance. Although aerobic capacity evaluation used to be expensive, critical speed (CS is easy and non - expensive tool capable to make this measurement. Thus, the aim of this study was evaluate the effects of linear periodization in CS on well - trained young swimmers. Sixteen athletes (age: 14.06  1.22 years, height: 163.52  10.99 cm, weight: 57.4  12.7 kg, body mass index: 21.24  37; 7 ♀, were underwent to a linear macrocycle training with 23 weeks divided in four mesocycles: general endurance (i.e., 4 weeks, specific endurance (i.e., 8 weeks, competitive (i.e., 7 weeks and taper (i.e., 4 weeks. Results showed significantly improve on CS after competitive and taper mesocycle phases, which was composed by higher training intensity in comparison with other macrocycle phases. Therefore, the results of the present study indicate a collaboration of mesocycle intensity on the cumulative effects of linear periodization in CS improve on young swimmers.

  18. Thermal stability of antiparasitic macrocyclic lactones milk residues during industrial processing.

    Science.gov (United States)

    Imperiale, F A; Farias, C; Pis, A; Sallovitz, J M; Lifschitz, A; Lanusse, C

    2009-01-01

    The chemical stability of residues of different antiparasitic macrocyclic lactone compounds in milk subjected to thermal treatment was assessed. Concentrations of ivermectin (IVM), moxidectin (MXD) and eprinomectin (EPM) in sheep milk, equivalent to those measured in vivo in milk excretion studies, were subjected to 65 degrees C over 30 min or to 75 degrees C for 15 s. Residue concentrations of IVM, MXD and EPM in milk were measured by high-performance liquid chromatography (HPLC) (fluorescence detection) before and after heat treatment of the drug-fortified milk samples. No evidence of chemical loss was obtained in either of the thermal treatments under evaluation. The stability of the parent compounds in milk was evidenced by the lack of bioconversion products (metabolites) after both thermal treatments. Only very minor changes on drug concentrations were observed at the end of the treatments, which fell within the limits of the variation of the validated analytical method. In conclusion, residue concentrations of macrocyclic lactones are unaffected by industrial-simulated milk thermal procedures. Based on the reported findings, it can be postulated that residue concentrations of IVM, MXD and EPM measured in raw sheep milk may be used to estimate consumer exposure and dietary intake for these veterinary drugs.

  19. Posterior preveneered stainless steel crowns: clinical performance after three years.

    Science.gov (United States)

    O'Connell, Anne C; Kratunova, Evelina; Leith, Rona

    2014-01-01

    The purpose of this study was to evaluate the clinical performance of posterior preveneered stainless steel crowns after three years. NuSmile crowns and Kinder Krowns were randomly allocated on paired molars using a split-mouth design. Variables such as fracture, wear, gingival health, and esthetics were recorded. (Pcrowns in 14 children. After three years, 53 percent of crowns were fracture free compared to 81 percent at one year. There was minimal esthetic impact for most fractures due to the location of the veneer fracture, but five crowns had extensive fracture. No difference was reported in the clinical performance between the two crown types. Fracture was more likely to occur where the adjacent tooth was missing. Parents reported a satisfaction rating of 8.3 out of 10. Clinical performance of both crown types was similar and successful for three years. Facing fracture occurred in 47 percent of crowns but had minimal impact on the esthetic value or parental satisfaction in the majority of cases. These crowns offer an esthetic alternative to the traditional stainless steel crown, but parents should be alerted to the possibility of veneer loss over time.

  20. Adhesive Cementation Promotes Higher Fatigue Resistance to Zirconia Crowns.

    Science.gov (United States)

    Campos, F; Valandro, L F; Feitosa, S A; Kleverlaan, C J; Feilzer, A J; de Jager, N; Bottino, M A

    The aim of this study was to investigate the influence of the cementation strategy on the fatigue resistance of zirconia crowns. The null hypothesis was that the cementation strategy would not affect the fatigue resistance of the crowns. Seventy-five simplified molar tooth crown preparations were machined in glass fiber-filled epoxy resin. Zirconia crowns were designed (thickness=0.7 mm), milled by computer-aided design/computer-aided manufacturing, and sintered, as recommended. Crowns were cemented onto the resin preparations using five cementation strategies (n=15): ZP, luting with zinc phosphate cement; PN, luting with Panavia F resin cement; AL, air particle abrasion with alumina particles (125 μm) as the crown inner surface pretreatment + Panavia F; CJ, tribochemical silica coating as crown inner surface pretreatment + Panavia F; and GL, application of a thin layer of porcelain glaze followed by etching with hydrofluoric acid and silanization as crown inner surface pretreatment + Panavia F. Resin cement was activated for 30 seconds for each surface. Specimens were tested until fracture in a stepwise stress fatigue test (10,000 cycles in each step, 600 to 1400 N, frequency of 1.4 Hz). The mode of failure was analyzed by stereomicroscopy and scanning electron microscopy. Data were analyzed by Kaplan-Meier and Mantel-Cox (log rank) tests and a pairwise comparison (pzirconia layer. Finite element analysis showed the different stress distribution for the two models. Adhesive cementation of zirconia crowns improves fatigue resistance.

  1. Relation of Crown Width to Tree Diameter In Some Upland Hardwood Stands of Southern Illinois

    Science.gov (United States)

    Leon S. Minckler; Samuel F. Gingrich

    1970-01-01

    Crown width-d.b.h. relationships in well stocked, uneven-aged stands of oak and hickory were similar to those for open-grown trees and were independent of site, crown class, and species. The irregular crowns of forest grown trees interface and overlap, however, and measuring crown extensions to the branch tips tended to overestimate effective crown area

  2. 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

  3. 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

  4. Site-selective guest inclusion in molecular networks of butadiyne-bridged pyridino and benzeno square macrocycles on a surface.

    Science.gov (United States)

    Tahara, Kazukuni; Lei, Shengbin; Mamdouh, Wael; Yamaguchi, Yui; Ichikawa, Tomoyuki; Uji-I, Hiroshi; Sonoda, Motohiro; Hirose, Keiji; De Schryver, Frans C; De Feyter, Steven; Tobe, Yoshito

    2008-05-28

    We present here the formation of a modular 2D molecular network composed of two different types of square-shaped butadiyne-bridged macrocycles, having intrinsic molecular voids, aligned alternately at the solid-liquid interface. Site-selective inclusion of a guest cation took place at every other molecular void in the molecular network with two different recognition sites.

  5. 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.

  6. Crowns cemented on crown preparations lacking geometric resistance form. Part II: effect of cement.

    Science.gov (United States)

    Proussaefs, Periklis

    2004-03-01

    This study evaluated the effect of different cements on resistance to dislodgment of crowns cemented on preparations lacking geometric resistance form. A preparation that offered no geometric resistance form, with 20 degrees total occlusal convergence (TOC), 0.9 mm wide shoulder finish line, and a 2.5 mm axial wall height was created on an ivorine tooth using a milling machine. Ten metal test specimen die replicas and 10 standardized metal crowns with recipient sites for the application of external forces through a universal testing machine were fabricated. The crowns were cemented on the dies under 5 and 10 kg external loads, the marginal openings measured, loaded to dislodgment, and cleaned of cement. The process was repeated using zinc oxide and eugenol (ZOE), zinc phosphate (ZPh), resin modified glass ionomer (RMGI), and composite resin (CR) cements. Marginal openings under 5 kg cementation loads were 74.63 (+/-15.04) for ZOE, 75.98 (+/-18.20) microm for ZPh, 98.58 (+/-22.62) microm for RMGI, and 105.82 (+/-20.07) microm for CR cements respectively; under 10 kg cementation loads they were 57.62 (+/-15.86) microm, 59.55 (+/-15.41) microm, 95.00 (+/-19.52) microm, 101.30 (+/-12.52) microm respectively. Oblique dislodgment forces, measured with a Universal testing machine, were 40.18 (+/- 6.76) N for ZOE, 215.65 (+/-45.79) N for ZPh, 165.43 (+/-19.53) N for RMGI, and 181.54 (+/-30.75) N for CR respectively when crowns were cemented under 5 kg loads. The corresponding values for 10 kg loads were 38.62 (+/-4.19), 274.86 (+/-54.22), 139.70 (+/-21.71), and 160.40 (+/-21.21) respectively. Only zinc phosphate cement produced statistically enhanced resistance when crowns were cemented under 10 kg force (p value = 0.035). Under the conditions of the present study only crowns cemented with zinc phosphate displayed increased resistance to dislodgment on preparations lacking resistance form.

  7. 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 ...

  8. Short clinical crowns (SCC) – treatment considerations and techniques

    Science.gov (United States)

    Rahul, G. R.; Poduval, Soorya T.; Shetty, Karunakar

    2012-01-01

    When the clinical crowns of teeth are dimensionally inadequate, esthetically and biologically acceptable restoration of these dental units is difficult. Often an acceptable restoration cannot be accomplished without first surgically increasing the length of the existing clinical crowns; therefore, successful management requires an understanding of both the dental and periodontal parameters of treatment. The complications presented by teeth with short clinical crowns demand a comprehensive treatment plan and proper sequencing of therapy to ensure a satisfactory result. Visualization of the desired result is a prerequisite of successful therapy. This review examines the periodontal and restorative factors related to restoring teeth with short clinical crowns. Modes of therapy are usually combined to meet the biologic, restorative, and esthetic requirements imposed by short clinical crowns. In this study various methods for treating short clinical crowns are reviewed, the role that restoration margin location play in the maintenance of periodontal and dental symbiosis and the effects of violation of the supracrestal gingivae by improper full-coverage restorations has also been discussed. Key words:Short clinical crown, surgical crown lengthening, forced eruption, diagnostic wax up, alveoloplasty, gingivectomy. PMID:24558561

  9. Evaluation of wild Juglans species for crown gall resistance

    Science.gov (United States)

    Paradox, the most widely used rootstock in CA walnut production, is highly susceptible to the causal agent of crown gall (CG) Agrobacterium tumefaciens. The bacterial pathogen induces the formation of large tumors around the crown of the tree resulting in a reduction in both vigor and yield. If left...

  10. Gloss and Surface Roughness of Anterior Pediatric Zirconia Crowns.

    Science.gov (United States)

    Theriot, Adrien L; Frey, Gary N; Ontiveros, Joe C; Badger, Gary

    2017-09-15

    The purpose of this study was to determine gloss and surface roughness (Ra) of pediatric anterior zirconia crowns. Gloss of labial and lingual surfaces of pediatric anterior zirconia crowns from three manufacturers was measured on 20 specimens using a small area gloss meter on each. Ra (μm) was measured using a contact-type surface profilometer. Data were evaluated by analysis of variance and pair-wise comparison at the 0.05 level of significance. There were statistically significant interactions between surface location and crown type for both gloss and Ra scores. NuSmile had higher mean gloss scores and lower mean Ra scores than both Kinder Krowns and EZCrowns. Kinder Krowns showed lower mean gloss scores and higher Ra scores than other crown groups. Among all crowns, there was a trend of higher mean gloss paired with lower mean surface roughness, and lower mean gloss paired with higher mean Ra. Hand smoothed followed by mechanically polished zirconia crowns (NuSmile) displayed the highest mean gloss and lowest mean Ra compared to hybrid polishedglazed zirconia crowns (Kinder Krowns, EZCrowns). Of the hybrid polished-glazed zirconia crowns, Kinder Krowns displayed the lowest mean gloss and highest mean Ra.

  11. 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...

  12. Relationships among alfalfa resistance to Sclerotinia crown and ...

    African Journals Online (AJOL)

    Sclerotinia crown and stem rot (SCSR) of alfalfa caused by Sclerotinia trifoliorum is one of the main constraints for efficient alfalfa cultivation in temperate climate all over the world. The resistance of 200 alfalfa accessions to Sclerotinia crown and stem rot was evaluated during 2010 to 2011 in the field nursery established in ...

  13. Evaluation of Vertical Marginal Adaptation of Provisional Crowns by ...

    African Journals Online (AJOL)

    Objective: To investigate and compare the degree of vertical marginal discrepancy of four provisional crown materials by digital microscope. Materials and Methods: A total of 100 provisional crowns were fabricated on standardized resin dies by direct technique of provisional fabrication, using four different provisional ...

  14. Short clinical crowns (SCC) - treatment considerations and techniques.

    Science.gov (United States)

    Sharma, Ashu; Rahul, G R; Poduval, Soorya T; Shetty, Karunakar

    2012-10-01

    When the clinical crowns of teeth are dimensionally inadequate, esthetically and biologically acceptable restoration of these dental units is difficult. Often an acceptable restoration cannot be accomplished without first surgically increasing the length of the existing clinical crowns; therefore, successful management requires an understanding of both the dental and periodontal parameters of treatment. The complications presented by teeth with short clinical crowns demand a comprehensive treatment plan and proper sequencing of therapy to ensure a satisfactory result. Visualization of the desired result is a prerequisite of successful therapy. This review examines the periodontal and restorative factors related to restoring teeth with short clinical crowns. Modes of therapy are usually combined to meet the biologic, restorative, and esthetic requirements imposed by short clinical crowns. In this study various methods for treating short clinical crowns are reviewed, the role that restoration margin location play in the maintenance of periodontal and dental symbiosis and the effects of violation of the supracrestal gingivae by improper full-coverage restorations has also been discussed. Key words:Short clinical crown, surgical crown lengthening, forced eruption, diagnostic wax up, alveoloplasty, gingivectomy.

  15. 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 ...

  16. Crown ratio models for tropical rainforests species in Oban division ...

    African Journals Online (AJOL)

    Crown ratio (CR) is a characteristic used to describe the crown size, which is an important element of forest growth and yield. It is often used as an important predictor variable for tree-level growth equations. It indicates tree vigour and is an important habitat variable. It is often estimated using allometry. Modified versions of ...

  17. 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

  18. 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

  19. 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)

  20. [Clinical evaluation of zirconia crowns for single posterior teeth].

    Science.gov (United States)

    Chen, Yuanhua; Meng, Xiangfeng; Yu, Qing

    2014-06-01

    To observe and evaluate the clinical performance of zirconia crowns made by CEREC inLab computer aided design/computer aided manufacturing(CAD/CAM) for posterior teeth. A total of 242 patients were implanted with zirconia crowns fabricated by CEREC inLab CAD/CAM. The crowns were evaluated by Modified US Public Health Service criteria at baseline, 6, 12, 24, and 36 months. The chi-square test was used to analyze the survival rate. All but five crowns were evaluated by an independent evaluator at baseline, 6, 12, 24, and 36 months. The survival rate declined with time. The A score percentage was above 85% at 36 months. The single zirconia crowns fabricated by CEREC inLab CAD/CAM demonstrate satisfactory clinical performance during a short period.

  1. Structural Study of Mismatched Disila-Crown Ether Complexes

    Directory of Open Access Journals (Sweden)

    Kirsten Reuter

    2017-02-01

    Full Text Available Mismatched complexes of the alkali metals cations Li+ and Na+ were synthesized from 1,2-disila[18]crown-6 (1 and 2 and of K+ from 1,2,4,5-tetrasila[18]crown-6 (4. In these alkali metal complexes, not all crown ether O atoms participate in the coordination, which depicts the coordination ability of the C-, Si/C-, and Si-bonded O atoms. Furthermore, the inverse case—the coordination of the large Ba2+ ion by the relatively small ligand 1,2-disila[15]crown-5—was investigated, yielding the dinuclear complex 5. This structure represents a first outlook on sandwich complexes based on hybrid crown ethers.

  2. 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

  3. 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)

  4. EL CROWN HALL. CONTEXTO Y PROYECTO / The Crown Hall. Context and project

    Directory of Open Access Journals (Sweden)

    José Santatecla Fayós

    2010-05-01

    Full Text Available RESUMEN El artículo enmarca el edificio del Crown Hall en el contexto docente y arquitectónico de Mies van der Rohe. Revisa sus inicios en la Bauhaus con su primera intervención en un espacio docente para la Bauhaus de Berlín en 1932, así como su marcha a Estados Unidos, los planteamientos arquitectónicos del campus del IIT y el proyecto del Crown Hall. El texto incide en el estudio del proceso proyectual del Crown Hall analizando la evolución de su concepción arquitectónica a través de las diferentes versiones del proyecto. Se constata la transición desde los primeros planteamientos arquitectónicos de los edificios del campus del IIT proyectados por Mies hacia el planteamiento del gran espacio unitario del Crown Hall. Este proyecto se puede entender desde la creciente importancia de la estructura, la claridad constructiva y el manejo del acero y vidrio como únicos materiales de la imagen del edificio y el carácter flexible y unitario del espacio. Finalmente se hace referencia al concepto del “espacio universal” en la arquitectura de Mies, como un concepto abstracto que supera los de flexibilidad de uso o unidad espacial, insinuando, a modo de reflexión, las principales variables que definirían el espacio universal miesiano. SUMMARY The article showcases the Crown Hall building in the educational and architectural context of Mies van der Rohe. It reviews his beginnings in the Bauhaus with his first intervention in an educational space for the Bauhaus of Berlin in 1932, as well as his sojourn to the United States, and the architectural approaches to the IIT campus and the Crown Hall project. The text touches on the study of the planning process for the Crown Hall, analysing the evolution of its architectural conception, through the different versions of the project. The article covers the transition from the first architectural approaches for the IIT campus buildings, planned by Mies, to the approach of the large unitary space

  5. Diversity-oriented approach to macrocyclic cyclophane derivatives by Suzuki-Miyaura cross-coupling and olefin metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Chavan, Arjun S; Shaikh, Mobin

    2012-01-06

    Palladium-catalyzed Suzuki-Miyaura (SM) cross-coupling reaction with allylboronic acid pinacol ester and titanium assisted cross-metathesis (CM)/ring-closing metathesis (RCM) cascade has been used to synthesize macrocyclic cyclophane derivatives.

  6. 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.

  7. Head-to-tail macrocyclization of cysteine-free peptides using an o-aminoanilide linker.

    Science.gov (United States)

    Ohara, Takumi; Kaneda, Masato; Saito, Tomo; Fujii, Nobutaka; Ohno, Hiroaki; Oishi, Shinya

    2018-05-01

    A head-to-tail macrocyclization protocol for the preparation of cysteine-free cyclic peptides was investigated. The o-aminoanilide linker constructed in the peptide sequence by a standard Fmoc-based peptide synthesis procedure was subjected to nitrite-mediated activation under acidic conditions toward N-acyl benzotriazole as the active ester species. The subsequent cyclization smoothly proceeded by neutralization in the presence of additives such as 1-hydroxybenzotriazole (HOBt) and 1-hydroxy-7-azabenzotriazole (HOAt) to afford the expected cyclic pentapeptide, a CXCR4 antagonist. The cyclization efficiencies were dependent on the precursor open-chain sequence. The application of this step-wise activation-cyclization protocol to microflow reaction systems is also described. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. 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.

  9. HPLC Enantioseparation of Phenylcarbamic Acid Derivatives by Using Macrocyclic Chiral Stationary Phases

    Directory of Open Access Journals (Sweden)

    Hroboňová Katarína

    2016-06-01

    Full Text Available The HPLC by using chiral stationary phases based on macrocyclic antibiotics, dimethylphenyl carbamate cyklofructan 7 and β-cyclodextrin in terms of polar-organic separation mode (mobile phase methanol/acetonitrile/acetic acid/triethylamine were used for enantioseparation of alkoxy derivatives of phenylcarbamic acid. The effect of the analyte structures on the efficiency of enantioseparation was investigated. The most suitable stationary phase was teicoplanin aglycone, where the separations of the enantiomers were obtained (the resolution value from 0.65 to 2.90, depending on the structure of the analyte. Significant effect on the resolution of the enantiomers has position of alkoxy substituent in the hydrophobic part of the molecule. The enantiorecognition was achieved for 3-alkoxysubstituted derivatives.

  10. Cobalt(II)-selective membrane electrode based on a recently synthesized benzo-substituted macrocyclic diamide.

    Science.gov (United States)

    Shamsipur, M; Poursaberi, T; Rouhani, S; Niknam, K; Sharghi, H; Ganjali, M R

    2001-09-01

    A PVC-membrane electrode based on a recently synthesized 18-membered macrocyclic diamide is presented. The electrode reveals a Nernstian potentiometric response for Co2+ over a wide concentration range (2.0 x 10(-6)-1.0 x 10(-2) M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for Co2+ over a wide variety of other metal ions, and could be used over a wide pH range (3.0-8.0). The detection limit of the sensor is 6.0 x 10(-7) M. It was successfully applied to the direct determination and potentiometric titration of cobalt ion.

  11. 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.

  12. 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.

  13. [Comparison of adaptation of crowns of different lithium disilicate glass-ceramic].

    Science.gov (United States)

    Li, Kemeng; Ai, Hongjun; Yi, Zhe

    2016-05-01

    To evaluate the adaptation of different lithium disilicate glass-ceramic crown and whether different fabrication processes affect the adaptation of crowns. Thirty epoxy dies crowns were divided into 3 groups. They were cemented to domestic lithium disilicate glass-ceramic crowns in Group A, to IPS e.max CAD crowns in Group B and to IPS e.max Press crowns in Group C respectively. All crowns were cut by cutting machine. A confocal laser scanning microscope was used to measure the gap between crown tissue surface and die. There were significant differences in the three groups of measurement points(Pcrowns appeared to have clinically acceptable fit.

  14. 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.

  15. Snapshot and crystallographic observations of kinetic and thermodynamic products for NO2S2 macrocyclic complexes

    Directory of Open Access Journals (Sweden)

    In-Hyeok Park

    2018-01-01

    Full Text Available Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO2S2 macrocycle (L are reported. L reacts with copper(I iodide to give a mononuclear complex [Cu(L]2(Cu2I4·2CH2Cl2 (1, featuring three separate units. When cadmium(II iodide was reacted with L, an anion-coordinated complex [Cd(LI]2(Cd2I6·4CH3CN (2 with a needle-type crystal shape was formed as the kinetic product. Interestingly, when the needle-type kinetic product was left undisturbed in the mother solution it gradually transformed to the pseudo-dimer complex [Cd2(L2I2](Cd2I6 (3 with a brick-type crystal shape as the thermodynamic product. The dissolution–recrystallization process resulted in the elimination of the lattice solvent molecules (acetonitrile in 2 and the contraction of two neighboring macrocyclic complex units [Cd(LI]+, forming the pseudo-dimer 3 via an intermolecular Cd...I interaction between two monomers. For the entire process from kinetic to thermodynamic products, it was possible to obtain sequential photographic snapshots, single-crystal X-ray structures and powder X-ray diffraction patterns. For the copper(I and cadmium(II complexes, competitive NMR results agree with the solid-state data that show copper(I has a higher affinity for L than does cadmium(II.

  16. Fracture strength of lithium disilicate crowns compared to polymer-infiltrated ceramic-network and zirconia reinforced lithium silicate crowns.

    Science.gov (United States)

    Sieper, Kim; Wille, Sebastian; Kern, Matthias

    2017-10-01

    The aim of this study was to evaluate the fracture strength of crowns made from current CAD/CAM materials. In addition the influence of crown thickness and chewing simulation on the fracture strength was evaluated. Crowns were fabricated from lithium disilicate, zirconia reinforced lithium silicate (ZLS-ceramic) and a polymer-infiltrated ceramic-network (PICN) with an occlusal thickness of 1.0mm or 1.5mm, respectively (n=16). Crowns were cemented on composite dies. Subgroups of eight specimens were loaded with 5kg in a chewing simulator for 1,200,000 cycles with thermal cycling. Finally, all specimens were loaded until fracture in a universal testing machine. Three-way ANOVA was used to detect statistical interaction. Differences regarding the materials were tested with two-way ANOVA, following one-way ANOVA and a post-hoc Tukey's-Test. All crowns survived the chewing simulation. The material had a significant influence on the fracture resistance (p≤0.05). Lithium disilicate achieved the highest values of fracture strength in almost all groups followed by ZLS-ceramic. PICN achieved the lowest values of fracture strength. Chewing simulation increased the fracture strength of thick lithium disilicate crown significantly. Greater occlusal thickness of all crown materials resulted in higher crown fracture strength before chewing simulation. After chewing simulation occlusal thickness of lithium disilicate and PICN crowns had no significant influence on the fracture strength. All crowns revealed fracture strength above the clinically expected loading forces. Therefore the durability of the tested CAD/CAM materials seems promising also in an occlusal thickness of 1.0mm. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. 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)

  18. Guided tooth preparation for a pediatric zirconia crown.

    Science.gov (United States)

    Lee, Ju-Hyoung

    2018-03-01

    Unesthetic primary incisors can produce negative self-perceptions in preschool-aged children. In recent years, because of increased esthetic demands, prefabricated zirconia crowns have become increasingly popular. However, zirconia crowns cannot be crimped, and the clinician must prepare the teeth to fit the zirconia crowns. Therefore, extended preparation and fitting times are necessary, especially for inexperienced practitioners. A 1- to 2-millimeter subgingival feather margin also is required. Gingival hemorrhage after subgingival preparation compromises the retention of zirconia crowns. In this clinical report, the author presents a step-by-step description of the clinical and laboratory procedures for restoring a discolored traumatized incisor with a zirconia crown. The author used a polyvinyl siloxane occlusal registration material as an impression material and made 2 identical casts. The author fabricated 3 reduction guides after prospective tooth preparation on the casts. The author rapidly prepared the discolored incisor with the reduction guides and ultrasonic burs. A zirconia crown provided an optimal esthetic result and gingival health. Because the reduction guides provided a visibility intraorally, fast tooth reduction, less trial placement, and passive adaptation of the crown were successful. Because the ultrasonic burs prevented gingival injuries, hemorrhage control was not necessary. The presented technique reduced the patient's discomfort and total chair time. Therefore, this alternative technique is helpful for inexperienced practitioners. Copyright © 2018 American Dental Association. Published by Elsevier Inc. All rights reserved.

  19. 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

  20. 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

  1. The repair of preveneered posterior stainless steel crowns.

    Science.gov (United States)

    Yilmaz, Yucel; Gurbuz, Taskin; Eyuboglu, Ozge; Belduz, Nihal

    2008-01-01

    This study's purposes were to determine the shear bond strength (SBS) for and to perform dye penetration (microleakage) and scanning electron microscopy (SEM) evaluations of preveneered posterior stainless steel crowns (SSCs) that were repaired using 2 different materials. Twenty-two crowns were used. They were stored in artificial saliva for 30 days and then thermocycled. A force was applied on the crowns' occlusal surfaces until the original veneer material appeared to be fractured. The fracture types and S8S values were recorded. The crowns were then repaired using Panavia opaque cement and Tetric Flow or Monoopaque and Tetric Flow. Twenty of the repaired crowns were subjected to dye penetration and SBS tests, and the remaining 2 were evaluated using SEM. Statistical analysis revealed no statistically significant differences in the results of either the S8S or the dye penetration test (P = .58 and P = 38, respectively). A statistically significant difference was found between original and repaired crowns regarding fracture extent (P = .02), but not failure type (P = .08). SEM evaluation showed that there was no observable gap at the interface of the original or repaired materials and the stainless steel base. Preveneered posterior stainless steel crowns may be repaired using either repair material types tested here.

  2. Clinical assessment of enamel wear caused by monolithic zirconia crowns.

    Science.gov (United States)

    Stober, T; Bermejo, J L; Schwindling, F S; Schmitter, M

    2016-08-01

    The purpose of this study was to measure enamel wear caused by antagonistic monolithic zirconia crowns and to compare this with enamel wear caused by contralateral natural antagonists. Twenty monolithic zirconia full molar crowns were placed in 20 patients. Patients with high activity of the masseter muscle at night (bruxism) were excluded. For analysis of wear, vinylpolysiloxane impressions were prepared after crown incorporation and at 6-, 12-, and 24-month follow-up. Wear of the occlusal contact areas of the crowns, of their natural antagonists, and of two contralateral natural antagonists (control teeth) was measured by use of plaster replicas and a 3D laser-scanning device. Differences of wear between the zirconia crown antagonists and the control teeth were investigated by means of two-sided paired Student's t-tests and linear regression analysis. After 2 years, mean vertical loss was 46 μm for enamel opposed to zirconia, 19-26 μm for contralateral control teeth and 14 μm for zirconia crowns. Maximum vertical loss was 151 μm for enamel opposed to zirconia, 75-115 μm for control teeth and 60 μm for zirconia crowns. Statistical analysis revealed significant differences between wear of enamel by zirconia-opposed teeth and by control teeth. Gender, which significantly affected wear, was identified as a possible confounder. Monolithic zirconia crowns generated more wear of opposed enamel than did natural teeth. Because of the greater wear caused by other dental ceramics, the use of monolithic zirconia crowns may be justified. © 2016 John Wiley & Sons Ltd.

  3. Retention of cast crown copings cemented to implant abutments.

    Science.gov (United States)

    Dudley, J E; Richards, L C; Abbott, J R

    2008-12-01

    The cementation of crowns to dental implant abutments is an accepted form of crown retention that requires consideration of the properties of available cements within the applied clinical context. Dental luting agents are exposed to a number of stressors that may reduce crown retention in vivo, not the least of which is occlusal loading. This study investigated the influence of compressive cyclic loading on the physical retention of cast crown copings cemented to implant abutments. Cast crown copings were cemented to Straumann synOcta titanium implant abutments with three different readily used and available cements. Specimens were placed in a humidifier, thermocycled and subjected to one of four quantities of compressive cyclic loading. The uniaxial tensile force required to remove the cast crown copings was then recorded. The mean retention values for crown copings cemented with Panavia-F cement were statistically significantly greater than both KetacCem and TempBond non-eugenol cements at each compressive cyclic loading quantity. KetacCem and TempBond non-eugenol cements produced relatively low mean retention values that were not statistically significantly different at each quantity of compressive cyclic loading. Compressive cyclic loading had a statistically significant effect on Panavia-F specimens alone, but increased loading quantities produced no further statistically significant difference in mean retention. Within the limitations of the current in vitro conditions employed in this study, the retention of cast crown copings cemented to Straumann synOcta implant abutments with a resin, glass ionomer and temporary cement was significantly affected by cement type but not compressive cyclic loading. Resin cement is the cement of choice for the definitive non-retrievable cementation of cast crown copings to Straumann synOcta implant abutments out of the three cements tested.

  4. Survival Predictions of Ceramic Crowns Using Statistical Fracture Mechanics.

    Science.gov (United States)

    Nasrin, S; Katsube, N; Seghi, R R; Rokhlin, S I

    2017-05-01

    This work establishes a survival probability methodology for interface-initiated fatigue failures of monolithic ceramic crowns under simulated masticatory loading. A complete 3-dimensional (3D) finite element analysis model of a minimally reduced molar crown was developed using commercially available hardware and software. Estimates of material surface flaw distributions and fatigue parameters for 3 reinforced glass-ceramics (fluormica [FM], leucite [LR], and lithium disilicate [LD]) and a dense sintered yttrium-stabilized zirconia (YZ) were obtained from the literature and incorporated into the model. Utilizing the proposed fracture mechanics-based model, crown survival probability as a function of loading cycles was obtained from simulations performed on the 4 ceramic materials utilizing identical crown geometries and loading conditions. The weaker ceramic materials (FM and LR) resulted in lower survival rates than the more recently developed higher-strength ceramic materials (LD and YZ). The simulated 10-y survival rate of crowns fabricated from YZ was only slightly better than those fabricated from LD. In addition, 2 of the model crown systems (FM and LD) were expanded to determine regional-dependent failure probabilities. This analysis predicted that the LD-based crowns were more likely to fail from fractures initiating from margin areas, whereas the FM-based crowns showed a slightly higher probability of failure from fractures initiating from the occlusal table below the contact areas. These 2 predicted fracture initiation locations have some agreement with reported fractographic analyses of failed crowns. In this model, we considered the maximum tensile stress tangential to the interfacial surface, as opposed to the more universally reported maximum principal stress, because it more directly impacts crack propagation. While the accuracy of these predictions needs to be experimentally verified, the model can provide a fundamental understanding of the

  5. Preventive and conservative prosthodontic treatment using overdenture and Richmond crown

    Directory of Open Access Journals (Sweden)

    Jevin Stivie Cialy

    2016-12-01

    Full Text Available Prosthodontic treatment aims to restore the chewing function (rehabilitation and to prevent tooth decay and bone resorption (preventive and conservative. As an example, treatment by overdenture and Richmond crown. Overdenture is a partial or complete removable denture covered and supported by one or more teeth, the tooth roots and/or dental implants. Richmond crown is fixed denture by post and crown system, in which the post part goes into the root canal and its crown covers the entire of original tooth crown surface. By retaining the original teeth and/or roots, it could improve the stability and retention of the denture, and defend proprioseptic of teeth and vertical dimensions. To provide information about preventive prosthodontic treatment and prevention by using overdenture and Richmond crown. Case Report: A 50 year old woman only has 44 teeth on the mandible which is indicated for the overdenture construction and loss teeth 13, 14, 17 and 27 on the maxilla with deep caries in teeth 22 which is indicated for a removable partial denture (RPDs construction by Richmond crown gear 22. On an early stage study, printing models is done. Then treatment of the root canal on teeth 22 and 44, followed by root canal preparation, core construction (cast post and Richmond crown on tooth 22 and bareroot preparation on tooth 44 for overdenture construction. The procedure followed by printing, recording bite to insertion. Choosing treatment either overdenture or Richmond crown is very important because it could mantain remain original teeth, thus it can help to improve the retention and stabilization.

  6. Lanthanide crown ether complexes of p-sulfonatocalix[5]arene.

    Science.gov (United States)

    Dalgarno, Scott J; Hardie, Michaele J; Warren, John E; Raston, Colin L

    2004-08-21

    Two types of arrays are formed in water involving aza-crown ethers, p-sulfonatocalix[5]arene and europium(III) ions. One is a co-ordination polymer connecting calixarenes, sodium ions and lanthanide ions based on "ferris wheel" moieties incorporating aza-18-crown-6 and sodium ions. The second structure is a host-guest arrangement with di-protonated diaza-18-crown-6 in the cavity of the calixarenes as part of secondary coordination spheres of aquated europium(iii) ions.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ather, Amber; Ather, Hunaiza; Sheth, Sanket Milan; Muliya, Vidya Saraswathi [Manipal College of Dental Sciences, Manipal (Korea, Republic of)

    2012-09-15

    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. Reduction of HCCI combustion noise through piston crown design

    DEFF Research Database (Denmark)

    Pedersen, Troels Dyhr; Schramm, Jesper

    2010-01-01

    Seven shapes of piston crowns have been evaluated for their ability to reduce HCCI knock and transmission of combustion noise to the engine. The performance of each piston crown was evaluated with measurements of cylinder pressure, engine vibration and acoustic sound pressure measured one meter....... 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...... reduction as well as heat losses....

  9. One novel 1D coordination polymer with parallel dinuclear copper(II) macrocyclic platforms bridged by trans dimeric half-water molecules and two dinuclear copper(II) macrocyclic complexes with different coordination geometry obtained from different solvents

    Science.gov (United States)

    Chu, Zhaolian; You, Wei; Huang, Wei

    2009-02-01

    Three dinuclear copper(II) macrocyclic complexes, formulated as [Cu 2L(N 3) 2(0.5H 2O) 2] n ( 1), [Cu 2L(ClO 4) 2(CH 3CH 2OH)] ( 2) and [Cu 2L(CH 3OH) 2](ClO 4) 2 ( 3) (LH 2 = [2+2] Schiff base macrocyclic ligand condensed from 4-chloro-2,6-diformylphenol and 1,3-diaminopropane), have been prepared and determined by X-ray single-crystal diffraction. Complex 1 shows two six-coordinate Cu(II) centers in which two monodentate N3- anions and two half-water molecules are bonded at the apical positions in the trans configuration. Furthermore, the dimeric half-water molecules serve as a μ2-bridge linking adjacent macrocyclic units together with the multiple O sbnd H…N hydrogen bonds with azide anions, forming a novel 1D chain-like coordination polymer. Complexes 2 and 3 are obtained from different solvents (ethanol and methanol) and they can be converted into each other. The molecular structures and packing mode of 2 and 3 are different where six-coordinate and five-coordinate copper(II) centers are present, respectively.

  10. Retention force of secondary crowns to copings after temporary cementation: the effect of crown material and luting agent.

    Science.gov (United States)

    Mundt, Torsten; Heinemann, Friedhelm; Golecki, Gudrun; Schwahn, Christian; Biffar, Reiner

    2010-12-01

    Tooth-implant supported restorations can be temporarily cemented if the natural abutments are protected by permanently cemented copings. This in vitro study investigated the retention forces of pure titanium crowns to milled titanium alloy copings and of cobalt-chromium crowns to copings made of electroplated gold after cementation with different luting agents. Five specimens per group were cemented with acrylic-urethane cement (inner crown surface preisolated with petroleum jelly) and provisional zinc oxide cement. The retention was measured using a universal testing machine and a dental device for crown removal. The differences between groups were compared using analysis of variance. The pull-off forces for the cobalt-chromium secondary crowns cemented on gold copings using zinc oxide cement were significantly higher (mean=144.5 N) than the other crown-cement combinations (32.2-54.4 N), which showed no significant differences in the retention force. The impulse number and magnitude of the dental device was usually low and showed no substantial differences between the crown-cement combinations. It can be concluded that the results of the clinical removal method for prostheses differ from the results of the pull-off test. The question which luting agent is the better choice for retrievable restorations remains unanswered without further clinical and laboratory studies.

  11. A Review on the Toxicity and Non-Target Effects of Macrocyclic Lactones in Terrestrial and Aquatic Environments

    OpenAIRE

    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 ma...

  12. Introduction of axial chirality at a spiro carbon atom in the synthesis of pentaerythritol-imine macrocycles.

    Science.gov (United States)

    Grajewski, J; Piotrowska, K; Zgorzelak, M; Janiak, A; Biniek-Antosiak, K; Rychlewska, U; Gawronski, J

    2018-02-07

    Novel chiral macrocyclic polyimines with spiro carbon atoms are described. The key feature of the synthesis is the formation of an axially chiral quaternary carbon atom having four constitutionally identical substituents. This is possible either by the freezing of the labile conformation of a spiro-diboronate moiety or by the diastereomeric fitting of a conformationally stable spiro-acetal moiety into a chiral framework. A general model for the description of this type of axial chirality is proposed.

  13. 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

  14. Synthesis of Macrocyclic Organo-Peptide Hybrids from Ribosomal Polypeptide Precursors via CuAAC-/hydrazide-mediated cyclization

    OpenAIRE

    Smith, Jessica M.; Fasan, Rudi

    2015-01-01

    Macrocyclic peptides have attracted increasing attention as a potential new source of chemical probes and therapeutics. In particular, their conformationally restricted structure combined with a high degree of functional and stereochemical complexity make them promising scaffolds for targeting biomolecules with high affinity and selectivity. The exploration of this structural class rely on the availability of efficient and versatile methods for the generation of large and diversified librarie...

  15. 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.

  16. [Esthetic evaluation of Cerec 3D anterior crowns].

    Science.gov (United States)

    Yang, Jian; Feng, Hai-lan; Wei, Xiu-xia; Xing, Yan-xi; Jia, Lu; Zhou, Yong-sheng

    2012-03-27

    To observe the short-term effect of clinical application of Cerec 3D anterior crowns. A total of 16 patients were restored with 31 Cerec 3D anterior crowns. All restorations were stained before cementation. The evaluation started 1 week after luting. The restorations were examined in accordance with the modified US Public Health Service (USPHS) criteria at baseline and every 6 - 12 months. The observation period of 31 Cerec 3D anterior crowns varied from 8 to 33 months. The mean observation period was 22 months. All restorations scored A or B by modified USPHS standard. And 22 out of 31 restorations scored A for all criteria while 8 restorations scored B in color matching. Slight differences of translucency and chroma could be observed. Between baseline and follow-up examinations, insignificant shift from A-to B-rating occurred. Cerec 3D anterior crowns may achieve favorable short-term esthetic effects.

  17. Probing supramolecular complexation of cetylpyridinium chloride with crown ethers

    Science.gov (United States)

    Saha, Subhadeep; Roy, Mahendra Nath

    2017-11-01

    Supramolecular complexations of cetylpyridinium chloride with three comparable cavity dimension based crown ethers, namely, dibenzo-18-crown-6, 18-crown-6 and dicyclohexano-18-crown-6 have been explored and adequately compared in acetonitrile with the help of conductivity in a series of temperatures to reveal the stoichiometry of the three host-guest complexes. Programme based mathematical treatment of the conductivity data affords association constants for complexations from which the thermodynamic parameters were derived for better comprehension about the process. The interactions at molecular level have been explained and decisively discussed by means of FT-IR and 1H NMR spectroscopic studies that demonstrate H-bond type interactions as the primarily force of attraction for the investigated supramolecular complexations.

  18. Luminescent Lariat Aza-Crown Ether Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2010-03-01

    Full Text Available Lariat ethers are interesting recognition motifs in supramolecular chemistry. The synthesis of a luminescent lariat aza-crown ether with a carboxyl group appended by azide-alkyne (Huisgen cycloaddition is presented.

  19. 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.

  20. 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

  1. 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...

  2. Macrocyclic-, polycyclic-, and nitro musks in cosmetics, household commodities and indoor dusts collected from Japan: implications for their human exposure.

    Science.gov (United States)

    Nakata, Haruhiko; Hinosaka, Mari; Yanagimoto, Hayato

    2015-01-01

    This paper reported the occurrence and concentrations of macrocyclic-, polycyclic- and nitro musks in cosmetics and household commodities collected from Japan. The high concentrations and detection frequencies of Musk T, habanolide, and exaltolides were found in commercial products, suggesting their large amounts of production and usage in Japan. Polycyclic musks, HHCB and OTNE, also showed high concentrations in cosmetics and products. The estimated dairy intakes of Musk T and HHCB by the dermal exposure to commercial products were 7.8 and 7.9 μg/kg/day in human, respectively, and perfume and body lotion are dominant exposure sources. We also analyzed synthetic musks in house dusts. Polycyclic musks, HHCB and OTNE, showed high concentrations in samples, but macrocyclic musks were detected only in a few samples, although these types of musks were highly detected in commercial products. This is probably due to easy-degradation of macrocyclic musks in indoor environment. The dairy intakes of HHCB by dust ingestions were 0.22 ng/kg/day in human, which were approximately five orders of magnitudes lower than those of dermal absorption from commercial household commodities. Copyright © 2014 Elsevier Inc. All rights reserved.

  3. 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

  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. Development of post-fire crown damage mortality thresholds in ponderosa pine

    Science.gov (United States)

    James F. Fowler; Carolyn Hull Sieg; Joel McMillin; Kurt K. Allen; Jose F. Negron; Linda L. Wadleigh; John A. Anhold; Ken E. Gibson

    2010-01-01

    Previous research has shown that crown scorch volume and crown consumption volume are the major predictors of post-fire mortality in ponderosa pine. In this study, we use piecewise logistic regression models of crown scorch data from 6633 trees in five wildfires from the Intermountain West to locate a mortality threshold at 88% scorch by volume for trees with no crown...

  6. Crown profile equations for stand-grown western hemlock trees in northwestern Oregon.

    Science.gov (United States)

    David D. Marshall; Gregory P. Johnson; David W. Hann

    2003-01-01

    Crown profile equations were developed for stand-grown western hemlock(Tsuga heterophylla (Raf.) Sarg.) in northwest Oregon. The profile model uses a segmented approach, dividing the crown into an upper and lower portion at the point of the largest crown width (LCW). The model explains about 86% of the variation in crown width when LCW is known but...

  7. 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....

  8. Adhesively luted, metal-free composite crowns after five years.

    Science.gov (United States)

    Lehmann, Franziska; Spiegl, Katrin; Eickemeyer, Grit; Rammelsberg, Peter

    2009-12-01

    The effect of location and preparation design of abutment teeth and of preparation design on the survival and complication rate of metal-free, adhesively luted composite crowns (Artglass, Heraeus Kulzer) and their clinical performance was investigated in this controlled, randomized, prospective clinical study. After randomization, 114 single crowns (68 posterior, 46 anterior) were prepared either with a 0.5 mm chamfer finishing line or with a 0.5 mm shoulder combined with occlusal reduction of at least 1.5 mm. Buildups were made with a composite material, using the corresponding dentin adhesive. Crowns were manufactured on stone dies and intraorally adhesively luted with resin cement. Follow-up examinations were conducted after 1 month and 1, 2, 3, and 5 years. Documentation included failures and complications, occlusal contacts, plaque accumulation and patients' rating of esthetics and functionality. After 5 years, data for 83 single crowns had been obtained. Within an observation period of 5 years, 18 complications occurred, including 13 major failures which resulted in replacement of the crowns, and 5 minor complications which could be repaired. All loosened crowns (n = 2) were successfully re-cemented. The Cox Regression did not reveal any effect of location or preparation design on complication rate. Calculation of the Kaplan-Meier survival curve on the basis of major failures indicated a probability of survival of 96% after 3 years and 88.5% after 5 years. Four Artglass crowns had no contact in static occlusion after 5 years and plaque accumulation was significantly higher than for control teeth. esthetic and functional evaluation by patients revealed that acceptance was high. Metal-free composite crowns may be recommended for long-term temporary use. However, the complication rate and the increased plaque accumulation restrict the indication for permanent restorations.

  9. Failure Probability of Three Designs of Zirconia Crowns.

    Science.gov (United States)

    Ramos, Gabriela Freitas; Monteiro, Evelyn Barbosa; Bottino, Marco Antonio; Zhang, Yu; Marques de Melo, Renata

    2015-01-01

    This study used a two-parameter Weibull analysis for evaluation of the lifespan of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. A sample of 60 first molars were selected and prepared for full-coverage crowns with three different designs (n = 20): traditional (crowns with zirconia framework covered with feldspathic porcelain), modified (crowns partially covered with veneering porcelain), and monolithic (full-contour zirconia crowns). All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100 N, 3 Hz) with a piston with a hemispherical tip (Ø = 6 mm) until the specimens failed or up to 2 × 10⁶ cycles. Every 500,000 cycles, the fatigue tests were interrupted and stereomicroscopy (10×) was used to inspect the specimens for damage. The authors performed Weibull analysis of interval data to calculate the number of failures in each interval. The types and numbers of failures according to the groups were: cracking (13 traditional, 6 modified) and chipping (4 traditional) of the feldspathic porcelain, followed by delamination (1 traditional) at the veneer/core interface and debonding (2 monolithic) at the cementation interface. Weibull parameters (β, scale; η, shape), with a two-sided confidence interval of 95%, were: traditional-1.25 and 0.9 × 10⁶ cycles; modified-0.58 and 11.7 × 10⁶ cycles; and monolithic-1.05 and 16.5 × 10⁶ cycles. Traditional crowns showed greater susceptibility to fatigue, the modified group presented higher propensity to early failures, and the monolithic group showed no susceptibility to fatigue. The modified and monolithic groups presented the highest number of crowns with no failures after the fatigue test. The three crown designs presented significantly different behaviors under fatigue. The modified and monolithic groups presented less probability of failure after 2 × 10⁶ cycles.

  10. Slow cooling protocol improves fatigue life of zirconia crowns.

    Science.gov (United States)

    Paula, Vitor G; Lorenzoni, Fabio C; Bonfante, Estevam A; Silva, Nelson R F A; Thompson, Van P; Bonfante, Gerson

    2015-02-01

    To compare the fatigue life and damage modes of zirconia crowns fabricated with and without framework design modification when porcelain veneered using a fast or slow cooling protocol. Composite resin replicas of a first molar full crown preparation were fabricated. Zirconia copings were milled as conventional (0.5mm even thickness, Zr-C, n=20,) or modified (lingual margin of 1.0mm thickness, 2.0mm height connected to two proximal struts of 3.5mm height, Zr-M, n=20). These groups were subdivided (n=10 each) according to the veneer cooling protocol employed: fast cooling (Zr-CFast and Zr-MFast) and slow cooling (Zr-CSlow and Zr-MSlow). Crowns were cemented and fatigued for 10(6) cycles in water. The number of cycles to failure was recorded and used to determine the interval databased 2-parameter probability Weibull distribution parameter Beta (β) and characteristic life value Eta (η). 2-parameter Weibull calculation presented β=5.53 and β=4.38 for Zr-MFast and Zr-CFast, respectively. Slow cooled crowns did not fail by completion of 10(6) cycles, thereby Weibayes calculation was applied. Increased fatigue life was observed for slow cooled crowns compared to fast cooled ones. Groups Zr-MFast and Zr-MSlow presented no statistical difference. Porcelain cohesive fractures were mainly observed in fast cooled groups. Slow cooled crowns presented in some instances inner cone cracks not reaching the zirconia/veneer interface. Improved fatigue life in tandem with the absence of porcelain fractures were observed in slow cooled crowns, regardless of framework design. Crowns fast cooled chiefly failed by porcelain cohesive fractures. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  11. Surgical crown lengthening: a periodontal and restorative interdisciplinary approach.

    Science.gov (United States)

    Parwani, Simran R; Parwani, Rajkumar N

    2014-01-01

    Surgical crown lengthening helps to provide an adequate retention form for proper tooth preparation, thus enabling dentists to create esthetically pleasing and healthy restorations. Long-term stability requires accurate diagnosis and development of a comprehensive treatment plan in each case. This sequence of events stresses the importance of communication between the restorative dentist and the periodontist. This article presents 2 cases that involve surgical crown lengthening (including mucoperiosteal flap and ostectomy) for the restoration of teeth.

  12. Mechanical performance of implant-supported posterior crowns.

    Science.gov (United States)

    de Kok, Paul; Kleverlaan, Cornelis J; de Jager, Niek; Kuijs, Ruud; Feilzer, Albert J

    2015-07-01

    The fracture of implant-supported restorations, especially of the veneering layer, is a common problem in dentistry. Monolithic ceramic or resin restorations might help solve this problem. The purpose of this in vitro study was to obtain additional insight into the risk of fracture of implant-supported restorations. Identical crowns (n=10) of 10 different ceramic and composite resin materials were cemented on conventional abutments on implant replicas embedded in polymethyl methacrylate blocks. The specimens were subjected to compressive load in a universal testing machine to record initial load to failure (ILF). Additionally, the flexural strength (FS), compressive strength (CS), and elastic modulus (E) of the investigated materials were determined. These results were used in a finite element analysis model of a composite resin and a lithium disilicate crown. Anatomic contour zirconia (Lava Plus) crowns had the highest ILF (6065 N), followed by lithium disilicate (IPS e.max) (2788 N) and the composite resin materials (Protemp 4, Majesty Flow, Telio CAD, Estenia C&B, Lava Ultimate, VITA Enamic) (2386 to 1935 N). Veneered zirconia (Lava) crowns showed the lowest ILF (1477 N). The highest FS, CS, and E were found for Lava Plus and IPS e.max. No direct relationship was found between ILF and the FS, CS, or E. The finite element analysis showed stresses that did not exceed the FS or CS of IPS e.max. The surface roughness of these crowns might have caused initial failure at relatively low stresses. In this laboratory study, monolithic implant-supported crowns showed a higher ILF than conventional veneered ceramic crowns. Monolithic ceramic restorations might perform better than composite resin crowns. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  13. Failure probability of three designs of zirconia crowns

    Science.gov (United States)

    Ramos, G. Freitas; Monteiro, E. Barbosa Carmona; Bottino, M.A.; Zhang, Y.; de Melo, R. Marques

    2015-01-01

    Objectives This study utilized a 2-parameter Weibull analysis for evaluation of lifetime of fully or partially porcelain-/glaze-veneered zirconia crowns after fatigue test. Methods Sixty first molars were selected and prepared for full-coverage crowns with three different designs(n = 20): Traditional –crowns with zirconia framework covered with feldspathic porcelain; Modified– crowns partially covered with veneering porcelain; and Monolithic–full-contour zirconia crowns. All specimens were treated with a glaze layer. Specimens were subjected to mechanical cycling (100N, 3Hz) with a piston with hemispherical tip (Ø=6 mm) until the specimens failed or up to 2×106 cycles. Every 500,000 cycles intervals, the fatigue tests were interrupted, and stereomicroscopy (10 X) was used to inspect the specimens for damage. We performed Weibull analysis of interval data to calculate the number of failures in each interval. Results The types and number of failures according to the groups were: cracking (Traditional-13, Modified-6) and chipping (Traditional-4) of the feldspathic porcelain, followed by delamination (Traditional-1) at the veneer/core interface and debonding (Monollithic-2) at the cementation interface. Weibull parameters (beta, scale; and eta, shape), with a two-sided confidence interval of 95%, were: Traditional – 1.25 and 0.9 × 106cycles; Modified– 0.58 and 11.7 × 106 cycles; and Monolithic – 1.05 and 16.5 × 106 cycles. Traditional crowns showed greater susceptibility to fatigue, the Modified group presented higher propensity to early failures, and the Monolithic group showed no susceptibility to fatigue. The Modified and Monolithic groups presented the highest number of crowns with no failures after the fatigue test. Conclusions The three crown designs presented significantly different behaviors under fatigue. The Modified and the Monolithic groups presented less probability to failure after 2×106cycles. PMID:26509988

  14. Variation in crown light utilization characteristics among tropical canopy trees.

    Science.gov (United States)

    Kitajima, Kaoru; Mulkey, Stephen S; Wright, S Joseph

    2005-02-01

    Light extinction through crowns of canopy trees determines light availability at lower levels within forests. The goal of this paper is the exploration of foliage distribution and light extinction in crowns of five canopy tree species in relation to their shoot architecture, leaf traits (mean leaf angle, life span, photosynthetic characteristics) and successional status (from pioneers to persistent). Light extinction was examined at three hierarchical levels of foliage organization, the whole crown, the outermost canopy and the individual shoots, in a tropical moist forest with direct canopy access with a tower crane. Photon flux density and cumulative leaf area index (LAI) were measured at intervals of 0.25-1 m along multiple vertical transects through three to five mature tree crowns of each species to estimate light extinction coefficients (K). Cecropia longipes, a pioneer species with the shortest leaf life span, had crown LAI <0.5. Among the remaining four species, crown LAI ranged from 2 to 8, and species with orthotropic terminal shoots exhibited lower light extinction coefficients (0.35) than those with plagiotropic shoots (0.53-0.80). Within each type, later successional species exhibited greater maximum LAI and total light extinction. A dense layer of leaves at the outermost crown of a late successional species resulted in an average light extinction of 61% within 0.5 m from the surface. In late successional species, leaf position within individual shoots does not predict the light availability at the individual leaf surface, which may explain their slow decline of photosynthetic capacity with leaf age and weak differentiation of sun and shade leaves. Later-successional tree crowns, especially those with orthotropic branches, exhibit lower light extinction coefficients, but greater total LAI and total light extinction, which contribute to their efficient use of light and competitive dominance.

  15. 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.

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

    Science.gov (United States)

    Kortegaard, H E; Anthony Knudsen, T; Dahl, S; Agger, J F G; Eriksen, T

    2015-04-01

    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. 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. 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 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 · 8% in dogs without pulp exposure (n = 133) resulting in a significant (relative risk, 109 · 5; P < 0 · 001) risk of periapical pathology in teeth with pulp exposure compared to teeth without pulp exposure. The high risk of periapical pathology observed in teeth with pulp exposure confirms that these teeth should not be neglected in affected dogs. © 2015 British Small Animal Veterinary Association.

  17. Antimicrobial efficacy of chemical disinfectants on contaminated full metal crowns.

    Science.gov (United States)

    Orsi, Iara Augusta; Villabona, Camilo Andrés; Kameoka, Eliana; Ferreira, Marly Christiènne C G; Ito, Izabel Yoko; Saravia, Marta Estela

    2010-01-01

    Prosthetic restorations that have been tried in the patient's mouth are potential sources of infection. In order to avoid cross-infection, protocols for infection control should be established in dental office and laboratory. This study evaluated the antimicrobial efficacy of disinfectants on full metal crowns contaminated with microorganisms. Full crowns cast in a Ni-Cr alloy were assigned to one control group (n=6) and 5 experimental groups (n=18). The crowns were placed in flat-bottom glass balloons and were autoclaved. A microbial suspension of each type of strain - S. aureus, P. aeruginosa, S. mutans, E. faecalis and C. albicans- was aseptically added to each experimental group, the crowns being allowed for contamination during 30 min. The contaminated specimens were placed into recipients with the chemical disinfectants (1% and 2% sodium hypochlorite and 2% glutaraldehyde) for 5, 10 and 15 min. Thereafter, the crowns were placed into tubes containing different broths and incubated at 35ºC. The control specimens were contaminated, immersed in distilled water for 20 min and cultured in Thioglycollate broth at 35ºC. Microbial growth assay was performed by qualitative visual examination after 48 h, 7 and 12 days. Microbial growth was noticed only in the control group. In the experimental groups, turbidity of the broths was not observed, regardless of the strains and immersion intervals, thus indicating absence of microbial growth. In conclusion, all chemical disinfectants were effective in preventing microbial growth onto full metal crowns.

  18. 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 ... 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...

  19. Fracture resistance and failure modes of CEREC endo-crowns and conventional post and core-supported CEREC crowns

    Directory of Open Access Journals (Sweden)

    Chia-Yu Chang

    2009-09-01

    Conclusion: The bonded ceramic endo-crowns showed a significantly higher fracture resistance than the classic reinforced and designed group and, therefore, offer a feasible alternative for severely damaged teeth.

  20. Evaluation of nitrogen-rich macrocyclic ligands for the chelation of therapeutic bismuth radioisotopes.

    Science.gov (United States)

    Wilson, Justin J; Ferrier, Maryline; Radchenko, Valery; Maassen, Joel R; Engle, Jonathan W; Batista, Enrique R; Martin, Richard L; Nortier, Francois M; Fassbender, Michael E; John, Kevin D; Birnbaum, Eva R

    2015-05-01

    The use of α-emitting isotopes for radionuclide therapy is a promising treatment strategy for small micro-metastatic disease. The radioisotope (213)Bi is a nuclide that has found substantial use for targeted α-therapy (TAT). The relatively unexplored aqueous chemistry of Bi(3+), however, hinders the development of bifunctional chelating agents that can successfully deliver these Bi radioisotopes to the tumor cells. Here, a novel series of nitrogen-rich macrocyclic ligands is explored for their potential use as Bi-selective chelating agents. The ligands, 1,4,7,10-tetrakis(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (L(py)), 1,4,7,10-tetrakis(3-pyridazylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyd)), 1,4,7,10-tetrakis(4-pyrimidylmethyl)-1,4,7,10-tetraazacyclododecane (L(pyr)), and 1,4,7,10-tetrakis(2-pyrazinylmethyl)-1,4,7,10-tetraazacyclododecane (L(pz)), were prepared by a previously reported method and investigated here for their abilities to bind Bi radioisotopes. The commercially available and commonly used ligands 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and N-[(R)-2-amino-3-(p-isothiocyanato-phenyl)propyl]-trans-(S,S)- cyclohexane-1,2-diamine-N,N,N',N",N"-pentaacetic acid (CHX-A''-DTPA) were also explored for comparative purposes. Radio-thin-layer chromatography (TLC) was used to measure the binding kinetics and stabilities of the complexes formed. The long-lived isotope, (207)Bi (t(1/2)=32 years), was used for these studies. Density functional theory (DFT) calculations were also employed to probe the ligand interactions with Bi(3+) and the generator parent ion Ac(3+). In contrast to DOTA and CHX-A''-DTPA, these nitrogen-rich macrocycles selectively chelate Bi(3+) in the presence of the parent isotope Ac(3+). Among the four tested, L(py) was found to exhibit optimal Bi(3+)-binding kinetics and complex stability. L(py) complexes Bi(3+) more rapidly than DOTA, yet the resulting complexes are of similar stability. DFT calculations

  1. Aza-macrocyclic complexes of the Group 1 cations - synthesis, structures and density functional theory study.

    Science.gov (United States)

    Dyke, John; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian; Bhakhoa, Hanusha; Ramasami, Ponnadurai; Rhyman, Lydia

    2015-08-21

    The Group 1 complexes, [M(Me6[18]aneN6)][BAr(F)] (M = Li-Cs; Me6[18]aneN6 = 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), are obtained in high yield by reaction of the macrocycle with M[BAr(F)] in anhydrous CH2Cl2 solution, and characterised spectroscopically ((1)H, (13)C{(1)H}, (7)Li, (23)Na, and (133)Cs NMR), by microanalysis and, for M = Li, K, and Rb, by single crystal X-ray analysis. The structures show N6-coordination to the metal ion; the small ionic radius for Li(+) leads to a puckered conformation. In contrast, the K(+) ion fits well into the N6 plane, with the [BAr(F)](-) anions above and below, leading to two K(+) species in the asymmetric unit (a hexagonal planar [K(Me6[18]aneN6)](+) cation and a '[K(Me6[18]aneN6)(κ(1)-BAr(F))2](-) anion', with long axial KF interactions). The Rb(+) ion sits above the N6 plane, with two long axial RbF interactions in one cation and two long, mutually cis RbF interactions in the other. The unusual sandwich cations, [M(Me3tacn)2](+) (M = Na, K; distorted octahedral, N6 donor set) and half-sandwich cations [Li(Me3tacn)(thf)](+) (distorted tetrahedron, N3O donor set), [Li(Me4cyclen)(OH2)](+), and [Na(Me4cyclen)(thf)](+) (both distorted square pyramids with N4O donor sets) were also prepared (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Density functional theory (DFT) calculations, using the BP86 and B3LYP functionals, show that the accessibility of the [M(Me3tacn)2](+) sandwich cations depends strongly on the M(+) ionic radius, such that it is sufficiently large to avoid steric clashing between the Me groups of the two rings, and small enough to avoid very acute N-M-N chelate angles. The calculations also show that coordination to the Group 1 cation involves significant donation of electron density from the p-orbitals on the N atoms of the macrocycle, rather than purely

  2. 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

  3. Next generation macrocyclic and acyclic cationic lipids for gene transfer: Synthesis and in vitro evaluation.

    Science.gov (United States)

    Jubeli, Emile; Maginty, Amanda B; Abdul Khalique, Nada; Raju, Liji; Abdulhai, Mohamad; Nicholson, David G; Larsen, Helge; Pungente, Michael D; Goldring, William P D

    2015-10-01

    Previously we reported the synthesis and in vitro evaluation of four novel, short-chain cationic lipid gene delivery vectors, characterized by acyclic or macrocyclic hydrophobic regions composed of, or derived from, two 7-carbon chains. Herein we describe a revised synthesis of an expanded library of related cationic lipids to include extended chain analogues, their formulation with plasmid DNA (pDNA) and in vitro delivery into Chinese hamster ovarian (CHO-K1) cells. The formulations were evaluated against each other based on structural differences in the hydrophobic domain and headgroup. Structurally the library is divided into four sets based on lipids derived from two 7- or two 11-carbon hydrophobic chains, C7 and C11 respectively, which possess either a dimethylamine or a trimethylamine derived headgroup. Each set includes four cationic lipids based on an acyclic or macrocyclic, saturated or unsaturated hydrophobic domain. All lipids were co-formulated with the commercial cationic lipid 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine (EPC) in a 1:1 molar ratio, along with one of two distinct neutral co-lipids, cholesterol or 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) in an overall cationic-to-neutral lipid molar ratio of 3:2. Binding of lipid formulations with DNA, and packing morphology associated with the individual lipid-DNA complexes were characterized by gel electrophoresis and small angle X-ray diffraction (SAXD), respectively. As a general trend, lipoplex formulations based on mismatched binary cationic lipids, composed of a shorter C7 lipid and the longer lipid EPC (C14), were generally associated with higher transfection efficiency and lower cytotoxicity than their more closely matched C11/EPC binary lipid formulation counterparts. Furthermore, the cyclic lipids gave transfection levels as high as or greater than their acyclic counterparts, and formulations with cholesterol exhibited higher transfection and lower cytotoxicity than those

  4. 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.

  5. Fracture load of monolithic CAD/CAM lithium disilicate ceramic crowns and veneered zirconia crowns as a posterior implant restoration.

    Science.gov (United States)

    Kim, Jee Hwan; Lee, Su-Jeong; Park, Jun Sub; Ryu, Jae Jun

    2013-02-01

    To compare the fracture load and failure mode of the monolithic lithium disilicate crown (e.max group) and 2 types of veneered zirconia crowns, hand layer (ZV group) and heat pressed (ZP group), as a posterior implant-supported restoration. A total of 24 all-ceramic crowns for molar tooth were fabricated using the computer-aided design/computer-assisted manufacture (CAD/CAM) system. The e.max group crowns and zirconia copings for ZV and ZP groups were fabricated using a Cerec milling unit. The ZV group was fabricated using a hand-layer veneering method, and the ZP group using a heat-pressing method. All crowns were luted to the abutments, which were connected to implant fixtures, using resin cement. Fracture load was measured using the universal testing machine, and the fracture surface was evaluated by scanning electron microscopy. The ZP group showed significantly higher fracture load (5229.3 N) compared with the e.max group (3852.1 N) and ZV group (3100.3 N). All fractures in the ZV group occurred in the veneered layer. Monolithic CAD/CAM lithium disilicate crowns are applicable to posterior implant-supported restorations because the fracture load was higher than the average occlusal force.

  6. Crown fracture: Failure load, stress distribution, and fractographic analysis.

    Science.gov (United States)

    Campos, Roberto E; Soares, Paulo V; Versluis, Antheunis; de O Júnior, Osmir Batista; Ambrosano, Gláucia M B; Nunes, Isabella Ferola

    2015-09-01

    The outcomes from load-to-failure tests may not be applicable to clinical situations. The purpose of this study was to critically evaluate the efficacy of load-to-failure tests in the investigation of the fracture load and pattern of metal-free crowns. Four groups were formed from 128 bovine roots restored with metal posts, resin cores, and feldspathic, leucite, or lithium disilicate ceramic systems or polymer crowns. Each group was divided into 4 (n=8) according to the cement: zinc phosphate, self-adhesive resin, autopolymerizing resin, and glass ionomer. Mean fracture loads from compressive tests were submitted to ANOVA and Tukey HSD test. Finite element and fractographic analyses were performed and associated with the fracture load and pattern. Significantly higher fracture load values were obtained for the lithium disilicate ceramic, but finite element and fractographic analyses showed that the cement effect could not be determined. The finite element analysis showed the cement likely affected the fracture pattern, confirmed that stresses in the cements were little affected by the crown materials, and found that the stressed conditions were lowest in the lithium disilicate compared with other crowns for all cement combinations. The stressed conditions in the crowns depended more on the adhesive properties than on the elastic modulus of the cement materials. The level of the stressed condition in the crowns at the occlusal surface was about the same or higher than along their cement interface, consistent with the fractography, which indicated fractures starting at the load point. Higher stress levels in the crowns corresponded with a lower number of catastrophic fractures, and higher stresses in the cements seemed to reduce the number of catastrophic fracture patterns. The highest stressed conditions occurred along the occlusal surface for crown materials with a low elastic modulus or in combination with adhesive cements. The method used was not appropriate

  7. DNA binding affinity of a macrocyclic copper(II) complex: Spectroscopic and molecular docking studies.

    Science.gov (United States)

    Shahabadi, Nahid; Hakimi, Mohammad; Morovati, Teimoor; Fatahi, Navid

    2017-08-03

    The interaction of a novel macrocyclic copper(II) complex, ([CuL(ClO 4 ) 2 ] that L is 1,3,6,10,12,15-hexaazatricyclo[13.3.1.1 6,10 ]eicosane) with calf thymus DNA (ct-DNA) was investigated by various physicochemical techniques and molecular docking at simulated physiological conditions (pH = 7.4). The absorption spectra of the Cu(II) complex with ct-DNA showed a marked hyperchroism with 10 nm blue shift. The intrinsic binding constant (K b ) was determined as 1.25 × 10 4 M -1 , which is more in keeping with the groove binding with DNA. Furthermore, competitive fluorimetric studies with Hoechst33258 have shown that Cu(II) complex exhibits the ability to displace the ct-DNA-bound Hoechst33258 indicating that it binds to ct-DNA in strong competition with Hoechst33258 for the groove binding. Also, no change in the relative viscosity of ct-DNA and fluorescence intensity of ct-DNA-MB complex in the present of Cu(II) complex is another evidence to groove binding. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrogen bonds and van der Waals interactions played major roles in the binding reaction. The experimental results were in agreement with the results obtained via molecular docking study.

  8. 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).

  9. 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)

  10. Macrocyclic cavitands cucurbit[n]urils: prospects for application in biochemistry, medicine and nanotechnology

    Science.gov (United States)

    Gerasko, O. A.; Kovalenko, E. A.; Fedin, V. P.

    2016-08-01

    The prospects of using the organic macrocyclic cavitands cucurbit[n]urils (CB[n]) and their derivatives in biochemistry, medicine and nanotechnology are considered. A combination of CB[n] characteristics, such as a rigid highly symmetrical structure, polarized hydrophilic portals, a rather large intramolecular hydrophobic cavity, as well as high resistance to thermolysis and corrosive media and low toxicity, account for a wide range of unique opportunities for the deliberate design of new functional materials, which may find application in various areas of modern chemistry and new technologies. Inclusion compounds of CB[n] with biologically active molecules demonstrate a high potential for the design of a new generation of prolonged action pharmaceuticals. The review presents the prospects for the application of CB[n] to manufacture unique materials, such as CB[n]-containing vesicles, films and surfaces, suitable for immobilization of various molecules and nanoparticles on their surface and for the separation of complex mixtures. Potential applications of CB[n]-modified electrodes and hydrogels are analyzed, and the use of CB[n] in proton-conducting materials and materials for the gas sorption and separation are discussed. The bibliography includes 164 references.

  11. One-dimensional self-assembly of phenylacetylene macrocycles: effect of peripheral substituents.

    Science.gov (United States)

    Li, Jie; Zhou, Wei; Yang, Jiping; Lang, Xiufeng; Huang, Pengcheng

    2013-04-01

    Tetra- and tri-substituted m-phenylacetylene macrocycles with diethylene glycol monoethyl ether (DEG) phenylether peripheral side chains (PAM 1 and PAM 1') were synthesized, and both of them could self-assemble into well-defined one-dimensional (1D) structures through two kinds of fabrication processing. The recrystallization approach led to similar microbelts for PAMs 1 and 1' with hundreds of microns in length, 2-4 μm in width, and 200-300 nm in thickness. But AFM, XRD, and spectrum characterizations indicated that the microbelts of PAM 1' had smaller intercolumnar distances and more favorable π-π stacking. Two different nanostructures were obtained through the other processing of solvent evaporation: nanobelts for PAM 1 and twisted nanorods for PAM 1'. The different molecular arrangement and nanostructures could be ascribed to the different molecular structures, especially the different positioning of the peripheral substituents. This research provides a potential control over the morphology and the structure of the 1D assembly by adjusting the molecular structure as well as the sample processing. Copyright © 2013 Elsevier Inc. All rights reserved.

  12. 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)

  13. 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.

  14. Unraveling the Multistimuli Responses of a Complex Dynamic System of Pseudopeptidic Macrocycles.

    Science.gov (United States)

    Valdivielso, Angel M; Puig-Castellví, Francesc; Atcher, Joan; Solà, Jordi; Tauler, Romà; Alfonso, Ignacio

    2017-08-10

    Dynamic combinatorial libraries (DCLs) are excellent benchmark models to study the stimuli-responsiveness of chemical networks. However, increasingly complex systems are difficult to analyze with simple data analysis methods, because many variables and connections must be considered for their full understanding. Here we propose the use of multivariate data analysis methods to bisect the evolution of a complex synthetic dynamic library of pseudopeptidic macrocycles, containing side chains with charges of different sign. Several stimuli (ionic strength, pH and the presence of a biogenic polyamine) were applied to the same dynamic chemical mixture, and the adaptation of the whole system was characterized by HPLC and analyzed with principal component analysis (PCA) and multivariate curve resolution-alternating least squares (MCR-ALS) methods. Both multivariate data analysis chemometric approaches are an excellent combination to extract both qualitative and semi-quantitative information about the adaptive process of the library upon the action of each stimulus. The resolution of the system with these chemometric tools proved to be especially useful when two inter-connected stimuli were combined in the same dynamic system. Our results demonstrate the utility of these two approaches for the analysis of complex dynamic chemical systems and open the way toward the application of these powerful tools in the emergent field of systems chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Noncovalent Interactions Accompanying Encapsulation of Resorcinol within Azacalix[4]pyridine Macrocycle.

    Science.gov (United States)

    Lande, Dipali N; Bhadane, Smita A; Gejji, Shridhar P

    2017-03-02

    Electronic structure and noncovalent interactions within the inclusion complexes of resorcinol and calix[4]pyridine (CXP[4]) or azacalix[4]pyridine (N-CXP[4]) macrocycles have been analyzed by employing hybrid M06-2X density functional theory. It has been demonstrated that substitution of a heteroatom (-NH-) at the bridging position of the CXP[4] alters the shape of the cavity from a "box-shaped" to funnel-like one. Penetration of resorcinol guest within the CXP[4] cavity renders a "butterfly-like" structure to the complex, whereas the N-CXP[4] complex reveals distorted geometry with the guest being nearer to one of the pyridine rings at the upper rim of the host. Underlying hydrogen bonding, π···π, and other weak interactions are characterized using the Quantum Theory of Atoms in Molecules (QTAIM) and Noncovalent Interactions Reduced Density Gradient (NCI-RDG) methods. The coexistence of multiple intermolecular interactions is envisaged through the frequency shifts of the characteristic -NH and -OH vibrations in their calculated vibrational spectra. The guest protons confined to the host cavity exhibit shielding, while those facilitating hydrogen bonding engender the downfield signals in their calculated 1 H NMR spectra.

  16. 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.

  17. New ventures in the genotoxic and cytotoxic effects of macrocyclic lactones, abamectin and ivermectin.

    Science.gov (United States)

    Molinari, G; Soloneski, S; Larramendy, M L

    2010-01-01

    Abamectin and Ivermectin are 2 closely related members of the Avermectin family of 16-membered macrocyclic lactones derived from the actinomycete Streptomyces avermectinius which exhibit extraordinary anthelmintic activity. They are used worldwide in veterinary and human medicine as well as in agriculture. In the present review we summarized the results published so far for estimating the genotoxicity and cytotoxicity exerted by both compounds in several cellular systems. Although both compounds do not induce in vitro and in vivo gene mutations in either bacterial or mammalian cells, there is no concrete evidence of a clear clastogenic effect exerted both in vitro and in vivo in mammalian cells. However, reports indicating that both anthelmintic agents are able to induce single DNA-strand breaks in vitro and inhibit cell growth either in vitro or in in vivo bioassays, are scarce. Taking into account the similarity of the genotoxicity and cytotoxicity exerted by both antibiotics, and that only Abamectin has been classified so far as a class II toxicity pesticide by the EPA, the necessity of reconsideration for a further hazard evaluation of Ivermectin by an international regulatory agency(ies) is strongly recommended. Copyright 2010 S. Karger AG, Basel.

  18. Ceramometal crowns and bridges. Focus on failures.

    Science.gov (United States)

    Bell, A M; Kurzeja, R; Gamberg, M G

    1985-10-01

    There are numerous factors that can have an adverse or beneficial effect upon the esthetic appearance of a ceramometal restoration. Some of these factors are beyond the influence of the dentist unless he or she is aware of them. As knowledgable practicing dentists, they have the ability to prescribe for their patients in such a manner as to achieve greater success and, in turn, greater patient acceptance and recognition. These are the rewards of a successful crown and bridge practice, and the ceramometal restoration is the basic state of the art prosthesis in present use. Knowing how to take a shade under the proper lighting conditions is generally well taught as part of the dental school curriculum, but the knowledge that shade guides are manufactured with built in idiosyncrasies of color variations from guide to guide is an enlightening experience. O'Brien of the Department of Dental Materials at the University of Michigan School of Dentistry clearly demonstrated the variabilities of color intensities between porcelain manufacturers. Laboratory technicians have been frustrated by the inconsistency of shades of porcelains from one lot number to another. It is now more fully understood that fluorescence is an important factor in patient satisfaction, as patients observe and have their restorations seen under differing lighting conditions. The type of alloy used in the ceramometal combination can have an effect upon the esthetic result. The wider use of silver-palladium alloys requires that the porcelain employed be of a nongreening nature, or else the final glazed prosthesis will give off a greenish cast. The ability of the opaque to block out the metal substructure while blending with the gingival and incisal shades eliminates the graying out, which can be esthetically objectionable to the patient. However, one of the most important considerations in aesthetic ceramometal restorations is the correct anatomy, placement, and harmonious blending with the oral and

  19. 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.

  20. The use of stainless steel crowns: a systematic literature review.

    Science.gov (United States)

    Seale, N Sue; Randall, Ros

    2015-01-01

    The purpose was to review the published literature on stainless steel crowns (SSCs) from 2002 to the present as an update to an earlier review published in 2002. Included were published papers on clinical studies, case series, and laboratory testing on SSCs (including esthetic SSCs and the Hall technique) in peer-reviewed journals. Study quality and strength of evidence presented were assessed for papers reporting clinical results for SSCs as a primary study outcome using a list of weighting criteria. Sixty-one papers fulfilled the inclusion criteria (24 papers on 22 clinical studies, three case reports, 21 reviews and surveys, and 13 laboratory testing reports on SSCs and esthetic preformed metal crowns for primary and permanent molar teeth). Ten clinical studies achieved weighting scores ranging from 68 percent to 26 percent, with the two highest scoring studies (68 percent and 63 percent) considered good quality. Within the confines of the studies reviewed, primary molar esthetic crowns and SSCs had superior clinical performance as restoratives for posterior primary teeth, and the Hall technique was shown to have validity. No clinical studies were available on zirconia crowns. Further well-designed prospective studies on primary molar esthetic crowns and the Hall technique are needed.

  1. 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.

  2. Effect of cements on fracture resistance of monolithic zirconia crowns

    Science.gov (United States)

    Nakamura, Keisuke; Mouhat, Mathieu; Nergård, John Magnus; Lægreid, Solveig Jenssen; Kanno, Taro; Milleding, Percy; Örtengren, Ulf

    2016-01-01

    Abstract Objectives The present study investigated the effect of cements on fracture resistance of monolithic zirconia crowns in relation to their compressive strength. Materials and methods Four different cements were tested: zinc phosphate cement (ZPC), glass-ionomer cement (GIC), self-adhesive resin-based cement (SRC) and resin-based cement (RC). RC was used in both dual cure mode (RC-D) and chemical cure mode (RC-C). First, the compressive strength of each cement was tested according to a standard (ISO 9917-1:2004). Second, load-to-failure test was performed to analyze the crown fracture resistance. CAD/CAM-produced monolithic zirconia crowns with a minimal thickness of 0.5 mm were prepared and cemented to dies with each cement. The crown–die samples were loaded until fracture. Results The compressive strength of SRC, RC-D and RC-C was significantly higher than those of ZPC and GIC (p crown between the groups. Conclusion The values achieved in the load-to-failure test suggest that monolithic zirconia crowns with a minimal thickness of 0.5 mm may have good resistance against fracture regardless of types of cements. PMID:27335900

  3. 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

  4. Fracture Strength After Fatigue Loading of Lithium Disilicate Pressed Zirconia Crowns.

    Science.gov (United States)

    Kim, So-Yeun; Choi, Jae-Won; Ju, Sung-Won; Ahn, Jin-Soo; Yoon, Mi-Jung; Huh, Jung-Bo

    2016-01-01

    The aim of this study was to evaluate the fracture resistance of fatigued lithium disilicate pressed zirconia crowns versus other ceramic crowns. Lithium disilicate pressed zirconia, fluorapatite pressed zirconia, monolithic lithium disilicate, and monolithic zirconia crowns were fabricated. Cyclic and static loadings were applied to the mesiobuccal cusp tip after thermocycling and fracture strengths were recorded. Fatigued lithium disilicate pressed zirconia crowns were found to have a fracture resistance of 9,117.81 ± 727.04 N, compared with 9,240.61 ± 887.21 N for monolithic zirconia crowns, 3,030.18 ± 1,505.83 N for fluorapatite pressed zirconia crowns, and 4,173.94 ± 877.46 N for monolithic lithium disilicate crowns (P = .001). This in vitro study shows that fatigued lithium disilicate pressed zirconia and monolithic zirconia crowns have better fracture resistance than fluorapatite pressed zirconia and monolithic lithium disilicate crowns.

  5. 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...

  6. “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.

  7. Chipping Resistance of Graded Zirconia Ceramics for Dental Crowns

    Science.gov (United States)

    Zhang, Y.; Chai, H.; Lee, J.J.-W.; Lawn, B.R.

    2012-01-01

    A serious drawback of veneering porcelains is a pronounced susceptibility to chipping. Glass-infiltrated dense zirconia structures can now be produced with esthetic quality, making them an attractive alternative. In this study, we examined the hypothesis that such infiltrated structures are much more chip-resistant than conventional porcelains, and at least as chip-resistant as non-infiltrated zirconia. A sharp indenter was used to produce chips in flat and anatomically correct glass-infiltrated zirconia crown materials, and critical loads were measured as a function of distance from the specimen edge (flat) or side wall (crown). Control data were obtained on zirconia specimens without infiltration and on crowns veneered with porcelains. The results confirmed that the resistance to chipping in graded zirconia is more than 4 times higher than that of porcelain-veneered zirconia and is at least as high as that of non-veneered zirconia. PMID:22232142

  8. Microleakage of core materials for complete cast gold crowns.

    Science.gov (United States)

    Tjan, A H; Chiu, J

    1989-06-01

    This study evaluated the microleakage patterns of complete cast-gold crowns cemented onto teeth rebuilt with pin-retained cores made from cast gold, amalgam, composite resin, and silver-reinforced glass ionomer by using three different cements (zinc phosphate, glass ionomer, and resin cement). Crowns cemented onto unrebuilt tooth preparations with zinc phosphate cement served as controls. The cemented specimens were thermocycled between 4 degrees and 50 degrees C in waterbaths. They were then embedded in epoxy resin and sectioned. The extent of marginal microleakage was evaluated with a stereomicroscope and scored. The findings indicated that the type of luting agent used appeared to affect microleakage more than the core material. No significant differences in the degree of microleakage were found under crowns cemented onto teeth rebuilt with the four core materials when cemented with the same luting cement.

  9. A zirconia implant-crown system: a case report.

    Science.gov (United States)

    Kohal, Ralf J; Klaus, Gerold

    2004-04-01

    Exposed metal crown margins in the porcelain-fused-to-metal technique might be an esthetic problem. Therefore, all-ceramic crown systems are used for restoring teeth and dental implants. In addition, the gray color of a titanium implant might hamper the esthetic appearance of the entire reconstruction in cases of thin peri-implant soft tissue or tissue retraction. To further improve the esthetic aspect of dental implants, efforts are undertaken to develop implant systems fabricated out of tooth-colored materials that are biocompatible and able to withstand masticatory forces. One such material may be zirconia. The present article presents a case in which an all-ceramic custom-made zirconia implant-crown system was used for the replacement of a single tooth.

  10. Retention of crowns cemented on implant abutments with temporary cements.

    Science.gov (United States)

    Nagasawa, Yuko; Hibino, Yasushi; Nakajima, Hiroshi

    2014-01-01

    This study was to examine the retentive force of crowns to implant abutments with commercial temporary cements. Six different temporary cements were investigated. Cast crowns were cemented to the abutments using each cement and their retentive forces to abutments were determined 7 or 28 days after cementing (n=10). The retentive force of the cements to abutments varied widely among the products [27-109 N (7-day), 18-80 N (28-days)]. The retentive force of all the cements was not reduced as the time elapsed, except for two products tested. The polycarboxylate cements and paste-mixing type eugenol-free cements revealed comparable retentive force after 28 days of storage. The powder-liquid type cements showed a positive correlation (pcement between the retentive force and compressive strength. Mechanical strength of temporary cements could not be a prominent predicting factor for retention of the crowns on the abutments.

  11. 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

  12. 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.

  13. 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.

  14. 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.)

  15. Immediate esthetic crown with a facet of the extracted element.

    Science.gov (United States)

    Di Giacomo, Giovanni de Almeida Prado; Magalhães, Amanda; Ajzen, Sergio

    2014-07-01

    The present report describes a case of implant loading with an immediate temporary crown. The buccal crown surface was removed from the extracted tooth to obtain an aesthetically satisfactory result. After periodontal treatment, tooth 21 appeared proclined and showed Grade 3 mobility, indicating the need for its extraction. The remaining bone was imaged using computed tomography, and virtual surgical planning was performed using these results. The implant was immediately loaded postextraction into the fresh alveolus without a graft and flap procedure. The temporary tooth, which was manufactured using the extracted buccal surface, was a simple, fast, and low cost procedure that produced an excellent esthetic outcome.

  16. Displacement of Monolithic Rubble-Mound Breakwater Crown-Walls

    DEFF Research Database (Denmark)

    Nørgaard, Jørgen Harck; Andersen, Lars Vabbersgaard; Andersen, Thomas Lykke

    2012-01-01

    of the accumulated sliding distance of crown-wall superstructures, which is in contrast to findings from previous similar studies on caisson breakwaters. The calculated sliding distance is approximately three times larger than the measured one when using the original one-dimensional model suggested in previous...... studies on caisson breakwaters, but correction terms are suggested in the present paper to obtain almost equal measured and estimated displacements. This is of great practical importance since many existing rubble-mound crown-walls are subjected to increasing wave loads due to rising sea water level from...

  17. 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.

  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. Anti-influenza activity of marchantins, macrocyclic bisbibenzyls contained in liverworts.

    Directory of Open Access Journals (Sweden)

    Yuma Iwai

    Full Text Available The H1N1 influenza A virus of swine-origin caused pandemics throughout the world in 2009 and the highly pathogenic H5N1 avian influenza virus has also caused epidemics in Southeast Asia in recent years. The threat of influenza A thus remains a serious global health issue and novel drugs that target these viruses are highly desirable. Influenza A possesses an endonuclease within its RNA polymerase which comprises PA, PB1 and PB2 subunits. To identify potential new anti-influenza compounds in our current study, we screened 33 different types of phytochemicals using a PA endonuclease inhibition assay in vitro and an anti-influenza A virus assay. The marchantins are macrocyclic bisbibenzyls found in liverworts, and plagiochin A and perrottetin F are marchantin-related phytochemicals. We found from our screen that marchantin A, B, E, plagiochin A and perrottetin F inhibit influenza PA endonuclease activity in vitro. These compounds have a 3,4-dihydroxyphenethyl group in common, indicating the importance of this moiety for the inhibition of PA endonuclease. Docking simulations of marchantin E with PA endonuclease suggest a putative "fitting and chelating model" as the mechanism underlying PA endonuclease inhibition. The docking amino acids are well conserved between influenza A and B. In a cultured cell system, marchantin E was further found to inhibit the growth of both H3N2 and H1N1 influenza A viruses, and marchantin A, E and perrotein F showed inhibitory properties towards the growth of influenza B. These marchantins also decreased the viral infectivity titer, with marchantin E showing the strongest activity in this assay. We additionally identified a chemical group that is conserved among different anti-influenza chemicals including marchantins, green tea catechins and dihydroxy phenethylphenylphthalimides. Our present results indicate that marchantins are candidate anti-influenza drugs and demonstrate the utility of the PA endonuclease assay in

  20. Evaluation of retention of cemented laser-sintered crowns on unmodified straight narrow implant abutments.

    Science.gov (United States)

    Kilicarslan, Mehmet Ali; Ozkan, Pelin

    2013-01-01

    A common problem with cemented crowns is inadequate retention at the crown-abutment interface. The aim of this study was to compare the retention of new laser-sintered cobalt-chromium alloy crowns to the retention of cobalt-chromium alloy crowns fabricated with a traditional casting technique with and without an alloy primer. Twenty-four metallic crowns per casting technique were fabricated, and surface roughness values were recorded with a profilometer. Alloy primer was applied to half the specimens, and all crowns were luted with resin cement. After 24 hours, specimens were subjected to tensile force application with a universal testing machine. The effect of the cement amount was evaluated with an analytic balance. The results were compared using the Kruskal-Wallis multiple-comparison test. The Spearman correlation was used to determine correlations between crown retention and cement weight. The laser-sintered crowns (2.72 μm) were rougher than conventionally cast crowns. The mean load to failure values were as follows: 455.10 ± 192.69 Ncm for conventional crowns, 565.52 ± 112.87 Ncm for conventional crowns with alloy primer, 534.78 ± 130.15 Ncm for laser-sintered crowns, and 678.60 ± 212.83 Ncm for laser-sintered crowns with alloy primer. Laser-sintered crowns (10.10 ± 2.15 mg) showed a significant difference in terms of cement weight compared with cast crowns. In addition, negative correlations were found for retention and cement weight between all groups, except for the laser-sintered group without alloy primer. Retentive forces were significantly higher for laser-sintered crowns than for conventionally cast crowns. An increase in the surface roughness and the application of alloy primers led to an increase in the adhesive bonding of resin cements to metal alloys. It was concluded that a reduction in cement weight improved retention.

  1. 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.

  2. Changes in retention force with electroplated copings on conical crowns: a comparison of gold and zirconia primary crowns.

    Science.gov (United States)

    Bayer, Stefan; Kraus, Dominik; Keilig, Ludger; Gölz, Lina; Stark, Helmut; Enkling, Norbert

    2012-01-01

    The aim of this study was to examine the wear behavior of conical crowns with electroplated gold copings that are used to connect implants and teeth to a removable denture. Gold alloy and zirconium dioxide ceramic crowns were compared. Fifteen crowns each were milled for two groups: gold alloy and zirconium dioxide. Each specimen had a 2-degree taper. The electroplated coping was established by direct electroforming. The retentive forces and the correlating distance during insertion and separation were measured after 10,000 wear cycles were applied. The wear testing was separated into a start phase, an initial wear phase, and the long-term wear period. The retention force value and the force-distance integral of the first 0.3 mm of each cycle were calculated. The changes in retention force and integral did not differ significantly between both groups in the start and the initial wear phase. No differences were seen in force development during the long-term wear period. Only the force-distance integral showed a significant difference: the median values of the gold crowns increased slightly, and they decreased slightly for the zirconia crowns. The median force values never fell below 6 N for gold and 4 N for zirconia. Within the limitations of this study, the tested conical crowns showed clinically acceptable retentive properties. As with other retentive elements for dentures, the specimens tested showed the greatest amount of change in retentive forces during the first 2,000 cycles. The development of retention force in both groups was not significantly different. However, the zirconia specimens showed reduced variability, which is preferable in clinical practice.

  3. Fluorescence Sensing Properties of Thiazolobenzo-crown Ether Incorporating Coumarin

    International Nuclear Information System (INIS)

    Lee, Sang Hoon; Helal, Aasif; Kim, Hong Seok

    2010-01-01

    A new coumarin-thiazolobenzo-crown ether based fluorogenic chemosensor BTC (1) was reported. The ion-selective binding properties of 1 with different alkali, alkaline earth metals and transitional metals were investigated in an ethanol- DMSO system. BTC (1) showed the highest binding constant toward Hg 2+ over Ag + , Pb 2+ and Cu 2+

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

    African Journals Online (AJOL)

    2018-04-04

    Apr 4, 2018 ... and porcelain‑based ceramic blocks, metal alloy blocks, and various composite ... Mete, et al.: Primary molar CAD/CAM crowns brittleness, tendency to fracturing, and attrition on the enamel of the antagonist tooth.[9‑13] To overcome its ..... Yilmaz A, Ozdemir CE, Yilmaz Y. A delayed hypersensitivity reaction ...

  5. 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 ...

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

    African Journals Online (AJOL)

    2018-04-04

    Apr 4, 2018 ... are used.[8]. Glass‑ceramic material that is widely used with. CAD/CAM technologies has both advantages such as the esthetic appearance, color stability, biocompatibility, and life‑long durability and disadvantages such as. Original Article. Introduction. Stainless steel crowns (SSCs) were introduced by.

  7. CAD/CAM technology for implant abutments, crowns, and superstructures.

    Science.gov (United States)

    Kapos, Theodoros; Evans, Christopher

    2014-01-01

    The aim of this systematic review was to compare implant prostheses fabricated by computer-assisted design and computer-assisted manufacturing (CAD/CAM) with conventionally fabricated implant prostheses when assessing esthetics, complications (biologic and mechanical), patient satisfaction, and economic factors. Electronic searches for clinical studies focusing on long-term follow-up were performed using the PubMed and Ovid search engines. Concentrating on the restorative aspect of the CAD/CAM technology applicable to implant dentistry, pertinent literature was divided into articles related to implant abutments, crowns, and frameworks. A total of 18 articles satisfied the inclusion criteria. Two articles reported on CAD/CAM crowns, six on abutments, and 10 on implant-supported CAD/CAM frameworks. The mean survival rate for CAD/CAM crowns was 98.85% and for CAD/CAM abutments 100%. The mean survival rate for CAD/CAM frameworks was 95.98%. Based on the current literature, CAD/CAM fabricated crowns, abutments, and frameworks demonstrate survival rates comparable to conventionally fabricated prostheses. Implant survival appears unaffected by fabrication technique. Since this technology encompasses several manufacturing variations, a new definition might be necessary to accurately define the processes under which the CAD/CAM restorations are fabricated. "Complete CAD/CAM product" where no or minimal manual intervention is employed could be a possible term.

  8. Evaluaton of Wild Juglans Species for Crown Gall Resistance

    Science.gov (United States)

    Crown Gall disease of walnut is caused by the ubiquitous soil-borne bacterium, Agrobacterium tumefaciens, which is able to transfer a specific piece of its own DNA into the genome of the plant host cell. The result of this genetic transformation is the autonomous undifferentiated massive growth of ...

  9. Loading capacity of zirconia implant supported hybrid ceramic crowns.

    Science.gov (United States)

    Rohr, Nadja; Coldea, Andrea; Zitzmann, Nicola U; Fischer, Jens

    2015-12-01

    Recently a polymer infiltrated hybrid ceramic was developed, which is characterized by a low elastic modulus and therefore may be considered as potential material for implant supported single crowns. The purpose of the study was to evaluate the loading capacity of hybrid ceramic single crowns on one-piece zirconia implants with respect to the cement type. Fracture load tests were performed on standardized molar crowns milled from hybrid ceramic or feldspar ceramic, cemented to zirconia implants with either machined or etched intaglio surface using four different resin composite cements. Flexure strength, elastic modulus, indirect tensile strength and compressive strength of the cements were measured. Statistical analysis was performed using two-way ANOVA (p=0.05). The hybrid ceramic exhibited statistically significant higher fracture load values than the feldspar ceramic. Fracture load values and compressive strength values of the respective cements were correlated. Highest fracture load values were achieved with an adhesive cement (1253±148N). Etching of the intaglio surface did not improve the fracture load. Loading capacity of hybrid ceramic single crowns on one-piece zirconia implants is superior to that of feldspar ceramic. To achieve maximal loading capacity for permanent cementation of full-ceramic restorations on zirconia implants, self-adhesive or adhesive cements with a high compressive strength should be used. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  10. Why do crown ethers activate enzymes in organic solvents?

    NARCIS (Netherlands)

    van Unen, D.J.; Engbersen, Johannes F.J.; Reinhoudt, David

    2002-01-01

    One of the major drawbacks of enzymes in nonaqueous solvents is that their activity is often dramatically low compared to that in water. This limitation can be largely overcome by crown ether treatment of enzymes. In this paper, we describe a number of carefully designed new experiments that have

  11. 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 ... (12.57%), distol surface attack 1,528 (12.22%) buccal surface attack 926 (7.40%), lingual surface attack 59 (0.47%) occlusal surface attack 6540 (52.32%).

  12. Bio-inspired ion selective crown-ether polymer membranes

    NARCIS (Netherlands)

    Tas, Sinem

    2016-01-01

    Development of unctional membranes that are capable of selectively recognizing and transporting ions have key importance for the recovery and separation of specific icons (e.d. K+, Li+, Na+) from multicomponent mixtures. In this thesis, new membrane materials based on crown ether-metal ion

  13. 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

  14. Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

    Science.gov (United States)

    Irvin, Jennifer A.; Stasko, Daniel; Fallis, Stephen; Guenthner, Andrew J.; Webber, Cynthia; Blackwell, John; Chvalun, Sergei N.

    2003-01-01

    We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

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

    African Journals Online (AJOL)

    The crown-of-thorns starfish Acanthaster planci is a major management issue on coral reefs and the exploring of effective control methods to the starfish is an interesting goal. In this study, the chemical constituent of the starfish were analyzed and the toxicity of the starfish was tested when it was used as mice diet.

  16. Towards an optimized method of olive tree crown volume measurement.

    Science.gov (United States)

    Miranda-Fuentes, Antonio; Llorens, Jordi; Gamarra-Diezma, Juan L; Gil-Ribes, Jesús A; Gil, Emilio

    2015-02-04

    Accurate crown characterization of large isolated olive trees is vital for adjusting spray doses in three-dimensional crop agriculture. Among the many methodologies available, laser sensors have proved to be the most reliable and accurate. However, their operation is time consuming and requires specialist knowledge and so a simpler crown characterization method is required. To this end, three methods were evaluated and compared with LiDAR measurements to determine their accuracy: Vertical Crown Projected Area method (VCPA), Ellipsoid Volume method (VE) and Tree Silhouette Volume method (VTS). Trials were performed in three different kinds of olive tree plantations: intensive, adapted one-trunked traditional and traditional. In total, 55 trees were characterized. Results show that all three methods are appropriate to estimate the crown volume, reaching high coefficients of determination: R2 = 0.783, 0.843 and 0.824 for VCPA, VE and VTS, respectively. However, discrepancies arise when evaluating tree plantations separately, especially for traditional trees. Here, correlations between LiDAR volume and other parameters showed that the Mean Vector calculated for VCPA method showed the highest correlation for traditional trees, thus its use in traditional plantations is highly recommended.

  17. Calix salophen crown ethers as receptors for neutral molecules

    NARCIS (Netherlands)

    Reichwein, A.M.; Reichwein, Arjen M.; Verboom, Willem; Harkema, Sybolt; Spek, Anthony L.; Reinhoudt, David

    1994-01-01

    The calix[4]arene based salophen crown ethers 7 and 8 were synthesized as lipophilic carriers for neutral molecules. The X-ray structures of the H2O, CH3OH and (CH3)2SO complexes of 8a have been determined.

  18. Diet of nesting African Crowned Eagles Stephanoaetus coronatus in ...

    African Journals Online (AJOL)

    The aim of this study was to investigate the species composition of prey caught in the forest, savanna and emerging habitats in which African Crowned Eagles Stephanoaetus coronatus breed in KwaZulu-Natal province, South Africa. At the 17 nest sites, the remains of 195 prey individuals were collected. The five dominant ...

  19. Notes on African Crowned Eagle Stephanoaetus coronatus diet in ...

    African Journals Online (AJOL)

    Our study reports on contrasts in prey items from African Crowned Eagle Stephanoaetus coronatus nesting in forest (n = 1) and savanna (n = 2) biomes in KwaZulu-Natal, South Africa. At least 12 taxa were identified at a forest nest, of which 92.1% were neonate/juvenile. Bovids and procaviids represented 73.7% and 19.6% ...

  20. Towards an Optimized Method of Olive Tree Crown Volume Measurement

    Science.gov (United States)

    Miranda-Fuentes, Antonio; Llorens, Jordi; Gamarra-Diezma, Juan L.; Gil-Ribes, Jesús A.; Gil, Emilio

    2015-01-01

    Accurate crown characterization of large isolated olive trees is vital for adjusting spray doses in three-dimensional crop agriculture. Among the many methodologies available, laser sensors have proved to be the most reliable and accurate. However, their operation is time consuming and requires specialist knowledge and so a simpler crown characterization method is required. To this end, three methods were evaluated and compared with LiDAR measurements to determine their accuracy: Vertical Crown Projected Area method (VCPA), Ellipsoid Volume method (VE) and Tree Silhouette Volume method (VTS). Trials were performed in three different kinds of olive tree plantations: intensive, adapted one-trunked traditional and traditional. In total, 55 trees were characterized. Results show that all three methods are appropriate to estimate the crown volume, reaching high coefficients of determination: R2 = 0.783, 0.843 and 0.824 for VCPA, VE and VTS, respectively. However, discrepancies arise when evaluating tree plantations separately, especially for traditional trees. Here, correlations between LiDAR volume and other parameters showed that the Mean Vector calculated for VCPA method showed the highest correlation for traditional trees, thus its use in traditional plantations is highly recommended. PMID:25658396

  1. Towards an Optimized Method of Olive Tree Crown Volume Measurement

    Directory of Open Access Journals (Sweden)

    Antonio Miranda-Fuentes

    2015-02-01

    Full Text Available Accurate crown characterization of large isolated olive trees is vital for adjusting spray doses in three-dimensional crop agriculture. Among the many methodologies available, laser sensors have proved to be the most reliable and accurate. However, their operation is time consuming and requires specialist knowledge and so a simpler crown characterization method is required. To this end, three methods were evaluated and compared with LiDAR measurements to determine their accuracy: Vertical Crown Projected Area method (VCPA, Ellipsoid Volume method (VE and Tree Silhouette Volume method (VTS. Trials were performed in three different kinds of olive tree plantations: intensive, adapted one-trunked traditional and traditional. In total, 55 trees were characterized. Results show that all three methods are appropriate to estimate the crown volume, reaching high coefficients of determination: R2 = 0.783, 0.843 and 0.824 for VCPA, VE and VTS, respectively. However, discrepancies arise when evaluating tree plantations separately, especially for traditional trees. Here, correlations between LiDAR volume and other parameters showed that the Mean Vector calculated for VCPA method showed the highest correlation for traditional trees, thus its use in traditional plantations is highly recommended.

  2. Protonation of benzo-18-crown-6: Extraction and DFT study

    Czech Academy of Sciences Publication Activity Database

    Toman, Petr; Makrlík, E.; Vaňura, P.; Kašička, Václav

    2011-01-01

    Roč. 225, č. 2 (2011), s. 265-270 ISSN 0942-9352 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505; CEZ:AV0Z40550506 Keywords : protonation * nitrobenzene * benzo-18-crown-6 Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.568, year: 2011

  3. Evaluating host resistance to Macrophomina crown rot in strawberry

    Science.gov (United States)

    Macrophomina crown rot, caused by the soilborne fungus Macrophomina phaseolina, is an emerging pathogen in California strawberry production. When established, the pathogen can cause extensive plant decline and mortality. Host resistance will be a critical tool for managing this disease and guiding ...

  4. Evolution of the mandibular third premolar crown in early Australopithecus.

    Science.gov (United States)

    Delezene, Lucas K; Kimbel, William H

    2011-06-01

    The Pliocene hominins Australopithecus anamensis and Australopithecus afarensis likely represent ancestor-descendent taxa--possibly an anagenetic lineage--and capture significant change in the morphology of the canine and mandibular third premolar (P(3)) crowns, dental elements that form the canine honing complex in nonhuman catarrhines. This study focuses on the P(3) crown, highlighting plesiomorphic features in A. anamensis. The A. afarensis P(3) crown, in contrast, is variable in its expression of apomorphic features that are characteristic of geologically younger hominins. Temporal variation characterizes each taxon as well. The A. anamensis P(3) from Allia Bay, Kenya expresses apomorphic character states, shared with A. afarensis, which are not seen in the older sample of A. anamensis P(3)s from Kanapoi, Kenya, while spatiotemporal differences in shape exist within the A. afarensis hypodigm. The accumulation of derived features in A. afarensis results in an increased level of P(3) molarisation. P(3) molarisation did not evolve concurrent with postcanine megadontia and neither did the appearance of derived aspects of P(3) occlusal form coincide with the loss of canine honing in hominins, which is apparent prior to the origin of the genus Australopithecus. A. afarensis P(3) variation reveals the independence of shape, size, and occlusal form. The evolution of the P(3) crown in early Australopithecus bridges the wide morphological gap that exists between geologically younger hominins on the one hand and extant apes and Ardipithecus on the other. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. New die design for dimensional accuracy assessment of crown castings.

    Science.gov (United States)

    Low, Danny

    2003-01-01

    The aim of this study was to introduce a newly designed die for ceramometal restoration, and to compare the dimensional accuracy with the traditional complete-crown design. Two methods of dimensional accuracy assessment, vertical axial discrepancy and transverse diametral percentage, were compared. Patterns were prepared from two different die designs--complete crown and ceramometal. Two investments available for titanium crown casting were used, Titavest CB and T-invest C & B. Titanium castings were made from each investment with a high-pressure casting machine. Vertical axial discrepancy of casting was determined by measuring the discrepancy for each set of wax patterns and their castings on the same die under a traveling microscope. Dimensional accuracy was expressed as vertical axial discrepancy and by transforming the vertical axial discrepancy into transverse diametral percentage. Both dies produced undersized castings with T-invest C & B and oversized castings with Titavest CB. Dimensional accuracy assessment of the two different types of crown casting design showed no significant difference in vertical axial discrepancy. Compared to the traditional transverse diametral percentage calculation, the vertical axial discrepancy assessment is independent of the die's dimensions. The two types of investment materials studied resulted in castings with different dimensional accuracies.

  6. Evaluation of Vertical Marginal Adaptation of Provisional Crowns by ...

    African Journals Online (AJOL)

    2018-01-30

    Jan 30, 2018 ... Department of Prosthetic Dental Sciences, College of Dentistry,. King Saud University, Riyadh, Kingdom of Saudi Arabia. E‑mail: malrifaiy@hotmail.com. How to cite this article: Al Rifaiy MQ. Evaluation of vertical marginal adaptation of provisional crowns by digital microscope. Niger J Clin Pract. 2017 ...

  7. Grey Crowned Cranes Balearica regulorum in urban areas of Uganda

    African Journals Online (AJOL)

    The greatest threat to birds in tropical Africa is habitat change; often a result of unsus- tainable agricultural practices (BirdLife International 2013a) and this certainly applies to Grey Crowned Cranes Balearica regulorum, whose primary breeding habitat — sea- sonal swamps — is increasingly being converted into cultivation ...

  8. Long-term survival of extensive amalgams and posterior crowns.

    Science.gov (United States)

    Smales, R J; Hawthorne, W S

    1997-01-01

    There is very little information available from private dental practices on the comparative survivals of extensive posterior amalgam restorations and posterior crowns placed in the same patient population. Therefore, the present retrospective study examined the performance of such restorations at three long-established Adelaide city practices. Life-table survival estimates were generated for 160 extensive amalgams, 96 cast gold crowns and 174 ceramometal crowns. The restorations were placed by 20 dentists at various times in 100 patients who attended the practices on a regular basis for around 25 years on average. There were no significant differences found in the survival times for both types of crowns, with around 70% still being present at 20 years. However, the median survival time for the extensive amalgams was much lower, at 14.6 years. Despite these differences in survival times, the extensive amalgam restorations survived for longer than is usually expected. In this present study, the survival findings have implications for the most cost-effective dental treatments of large lesions in posterior teeth.

  9. The impact of capture, domestication and trade on Black Crowned ...

    African Journals Online (AJOL)

    The inland delta of the Niger, a vast floodplain, is the only refuge of Black Crowned Cranes in Mali. This study, centred on the regions of Mopti, Tenenkou and Youwarou, aimed to: (1) census the number of cranes in the delta and in captivity in the towns of Mopti and Bamako; (2) examine exploitation at different levels (local ...

  10. 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

  11. 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)

  12. Autologous reattachment of complicated crown fractures using intra canal anchorage: Report of two cases

    OpenAIRE

    Kashetty Panchakshari Bharath; Raju Umaji Patil; Haalaswamy Vishwanath Kambalimath; Ashokan Alexander

    2015-01-01

    Crown fractures are most common form of dental trauma sustained by children and adolescents. Major portion of these crown fractures are uncomplicated. Complicated crown fractures though infrequent and account only 4-16%, is an enigma to any clinician. Autologus reattachment of the tooth fragment is a simple and conservative procedure in managing such crown fractures. The present article intends to report the successful clinical management of Autologus tooth fragment reattachment in two compli...

  13. Zinc, copper and nickel complexes of a macrocycle synthesized from pyridinedicarboxylic acid: A spectroscopic, thermal and theoretical study

    Directory of Open Access Journals (Sweden)

    Soleimani Esmaiel

    2017-01-01

    Full Text Available The metal(II ion complexes of a pentadentate macrocycle 1, namely 3,12-dioxa-6,9,18-triazabicyclo[12.3.1]octadeca-1(18,14,16-triene-2,13-dione are synthesized. This macrocycle is prepared from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with ethylenediamine and 1,2-dibromoethane. The reaction of 1 (L in methanol with MCl2.xH2O gave complexes with the general formula [M(LCl2] (where M= Ni(II 2, Cu(II 3 and Zn(II 4, respectively. The analysis of IR, 1H- and 13C-NMR spectral data of all complexes propose that 1 is bonded to metal(II ions through a nitrogen atom of pyridine ring, two nitrogen atoms of amine groups and two oxygen atoms of ester moieties. The thermal analysis indicated that there are no water molecules of hydration or coordinated in the structure of the complexes. Among these complexes, the Cu(II 3 complex demonstrated good antibacterial and antifungal activities. The molecular geometry, AIM atomic charge and frontier molecular orbitals of the compounds are investigated theoretically using DFT method. Based on the theoretical data of these complexes represented, a bipyramidal pentagonal arrangement can be envisaged in such a way that the N3O2 pentadentate donor sites form the planar pentagonal base of the bipyramid and the two Cl atoms occupy the vertexes.

  14. Synthesis and Biological Activities of Some New (Nα-Dinicotinoyl- bis-L-Leucyl Linear and Macrocyclic Peptides

    Directory of Open Access Journals (Sweden)

    Suzan Khayyat

    2014-07-01

    Full Text Available A series of linear and macrocyclic peptides 3–12 were synthesized using 3,5-pyridinedicarboxylic acid (1 as starting material and screened for their antimicrobial, anti-inflammatory and anticancer activities. Bis-ester 3 was prepared from 1 and L-leucine methyl ester. Hydrazinolysis and hydrolysis of dipeptide methyl ester 3 with hydrazine hydrate or 1 N sodium hydroxide afforded compounds 4 and 5, respectively. Cyclization of the dipeptide 5 with L-lysine methyl ester afforded cyclic pentapeptide ester 6. Compounds 7–9 were synthesized by reacting hydrazide 4 with phthalic anhydride, 1,8-naphthalene anhydride or acetophenone derivatives. Treatment of acid hydrazide 4 with aromatic aldehydes or tetraacid dianhydrides afforded the corresponding bis-dipeptide hydrazones 10a–e and macrocyclic peptides 11 and 12, respectively. The structures of newly synthesized compounds were confirmed by IR, 1H-NMR, MS spectral data and elemental analysis. The detailed synthesis, spectroscopic data, biological and pharmacological activities of the synthesized compounds was reported.

  15. The Eponymous Cofactors in Cytochrome P460s from Ammonia-Oxidizing Bacteria Are Iron Porphyrinoids Whose Macrocycles Are Dibasic.

    Science.gov (United States)

    Smith, Meghan A; Lancaster, Kyle M

    2018-01-23

    The enzymes hydroxylamine oxidoreductase and cytochrome (cyt) P460 contain related unconventional "heme P460" cofactors. These cofactors are unusual in their inclusion of nonstandard cross-links between amino acid side chains and the heme macrocycle. Mutagenesis studies performed on the Nitrosomonas europaea cyt P460 that remove its lysine-heme cross-link show that the cross-link is key to defining the spectroscopic properties and kinetic competence of the enzyme. However, exactly how this cross-link confers these features remains unclear. Here we report the 1.45 Å crystal structure of cyt P460 from Nitrosomonas sp. AL212 and conclude that the cross-link does not lead to a change in hybridization of the heme carbon participating in the cross-link but rather enforces structural distortions to the macrocycle away from planarity. Time-dependent density functional theory coupled to experimental structural and spectroscopic analysis suggest that this geometric distortion is sufficient to define the spectroscopic properties of the heme P460 cofactor and provide clues toward establishing a relationship between heme P460 electronic structure and function.

  16. 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.

  17. Synthesis, characterization and biological studies of homo and hetero-binuclear 13-membered pentaaza bis (macrocyclic) complexes

    Science.gov (United States)

    Zafar, Hina; Kareem, Abdul; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali

    2015-01-01

    A new series of homo and hetero binuclear 13-membered pentaaza bis (macrocyclic) complexes, [MM‧LX4], [M = Cu(II), M‧ = Cu(II), Co(II), Ni(II) and Sn(II); L = ligand and X = Cl or NO3] have been synthesized by the template reaction of dichloro/dinitrato diphenyl sulphone 1,3,6,9,12-tetra hydro pentaazacyclo pantane copper (II) complexes with formaldehyde, triethylenetetraamine, and respective metal salts in 1:2:1:1 molar ratio. The complexes have been characterized by elemental analyses, molar conductance measurements, ESI-mass, 1H, 13C and 119Sn NMR, IR, electronic and EPR spectral studies. The results of elemental analyses, ESI-mass and conductivity measurements confirmed the stoichiometry of the complexes while the characteristic absorption bands and resonance peaks in IR and NMR spectra confirmed the formation of macrocyclic frameworks of the complexes. These studies showed octahedral geometry around the metal ion. The thermal stability of copper complexes was also studied by TGA and DTA analyses. Some complexes of this series were also studied for their in vitro anticancer activity against cancer cells lines: Hep3B, MCF7, and HeLa. The recorded IC50 values for the tested complexes show moderate to good cytotoxicity against these cancer cell lines.

  18. In vitro performance of full-contour zirconia single crowns.

    Science.gov (United States)

    Beuer, Florian; Stimmelmayr, Michael; Gueth, Jan-Frederik; Edelhoff, Daniel; Naumann, Michael

    2012-04-01

    Zirconia based restorations exhibited high failure rates due to veneering-porcelain fractures. Milling to full-contour might be an alternative approach for zirconia restorations. The aim of this study was to evaluate full-contour zirconia crowns in terms of light-transmission, contact wear (restoration and antagonist) and load-bearing capacity. Powder build-up veneered zirconia substructures and CAD/CAM-veneered zirconia substructures served as controls. Four different kinds of crowns were fabricated on 12 metal dies: zirconia substructure with powder build-up porcelain (veneering technique), zirconia substructure with CAD/CAM generated veneering (sintering technique), full-contour zirconia glazed (glazed full-contour) and full-contour zirconia polished (polished full-contour). All crowns had the same dimensions. After light-transmission was measured the crowns were cemented on the corresponding metal dies. The specimens were loaded according to a special wear method in the chewing simulator (120,000 mechanical cycles, 5 kg load, 0.7 mm sliding movement, 320 thermocycles). Wear of the restoration and the antagonist were measured. All specimens were loaded until failure. One-way ANOVA and a LSD post-hoc test were used to compare data at a level of 5%. Polished full-contour showed significantly higher light transmission than the other groups (p=0.003; ANOVA). Polished full-contour exhibited significantly less contact wear at the restoration (p=0.01; ANOVA) and higher contact wear at the antagonist (p=0.016; ANOVA) compared to the other groups. Glazed full-contour zirconia showed similar contact wear at the antagonist compared to veneering technique (p=0.513, post-hoc LSD). Crowns with conventional veneering showed significantly lower load-bearing capacity (pzirconia to full-contour with glazed surface might be an alternative to traditionally veneered restorations. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  19. Unusual extraction behaviour of crown ether when intercalated in bentonite

    International Nuclear Information System (INIS)

    Sivaiah, M.V.; Krishna, R.M.; Murthy, G.S.; Venkatesan, K.A.; Sasidhar, P.

    2005-01-01

    Di-cyclo-hexano-18-crown-6 (DCH18C6) has been intercalated in bentonite and the product, Ben-Crown, characterized by micro-elemental analysis, TG-DTA analysis, X-ray diffraction and IR spectroscopy. The permanent negative charge present in the bentonite layer has been exploited for more efficient extraction of cesium and strontium by Ben-Crown at nitric acid concentrations (≤ 1.0 M) that gave only a meagre extraction when either DCH18C6 or bentonite alone were employed. The extraction of cesium and strontium has been investigated as a function of time, temperature, and the concentrations of nitric acid, metal ion and sodium nitrate. An unusual extraction phenomenon was observed at low concentrations of nitric acid (≤ 1.0 M) in the absence of any organo-philic agents. Rapid extraction of the metal ion was followed by the establishment of an equilibrium, which occurred after 150 min. Distribution coefficients (K d ) of 599 and 1007 ml g -1 were obtained, respectively, for the extraction of cesium and strontium from 0.1 M nitric acid by Ben-Crown; K d decreased with an increase in the temperature or in the concentrations of nitric acid and sodium nitrate. The extraction data were fitted by the Langmuir adsorption model and the apparent experimental exchange capacity obtained by linear regression analysis was in good agreement with the amount of crown ether (0.22 mmol g -1 ) intercalated in bentonite. The enthalpy change (ΔH 0 ) for the extraction of cesium and strontium was found to be exothermic. (authors)

  20. Bud development and shoot morphology in relation to crown location

    Science.gov (United States)

    Kukk, Maarja; Sõber, Anu

    2015-01-01

    Plant architecture is shaped by endogenous growth processes interacting with the local environment. The current study investigated crown development in young black alder trees, assessing the effects of local light conditions and branch height on individual bud mass and contents. In addition, we examined the characteristics of parent shoots [the cross-sectional area (CSA) of stem and total leaf area, shoot length, the number of nodes, the number and total mass of buds per shoot] and leaf–stem as well as bud–stem allometry, as several recent studies link bud development to hydraulic architecture. We sampled shoots from top branches and two lower-crown locations: one subjected to deep shade and the other resembling the upper branches in light availability. Sampling was carried out three times between mid-July and late October, spanning from the early stages of bud growth to dormancy. Individual bud mass and shoot characteristics varied in response to light conditions, whereas leaf–stem allometry depended on branch height, most likely compensating for the increasing length of hydraulic pathways. Despite the differences in individual bud mass, the number of preformed leaves varied little across the crown, indicating that the plasticity in shoot characteristics was mainly achieved by neoformation. The relationship between total bud mass and stem CSA scaled similarly across crown locations. However, scaling slopes gradually decreased throughout the sampling period, driven by bud rather than by stem growth. This suggests that the allometry of total bud mass and CSA of stem is regulated locally, instead of resulting from crown-level processes. PMID:26187607

  1. Comparative fracture strength analysis of Lava and Digident CAD/CAM zirconia ceramic crowns

    Science.gov (United States)

    Kwon, Taek-Ka; Pak, Hyun-Soon; Han, Jung-Suk; Lee, Jai-Bong; Kim, Sung-Hun

    2013-01-01

    PURPOSE All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. MATERIALS AND METHODS Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. RESULTS The mean fracture strengths were as follows: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (Pzirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. CONCLUSION The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain. PMID:23755332

  2. Fracture Strength of Aged Monolithic and Bilayer Zirconia-Based Crowns.

    Science.gov (United States)

    Lameira, Deborah Pacheco; Buarque e Silva, Wilkens Aurélio; Andrade e Silva, Frederico; De Souza, Grace M

    2015-01-01

    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.

  3. Enhancing a eucalypt crown condition indicator driven by high spatial and spectral resolution remote sensing imagery

    Science.gov (United States)

    Evans, Bradley; Lyons, Tom; Barber, Paul; Stone, Christine; Hardy, Giles

    2012-01-01

    Individual crown condition of Eucalyptus gomphocephala was assessed using two classification models to understand changes in forest health through space and time. Using high resolution (0.5 m) digital multispectral imagery, predictor variables were derived from textural and spectral variance of all pixels inside the crown area. The results estimate crown condition as a surrogate for tree health against the total crown health index. Crown condition is derived from combining ground-based crown assessment techniques of density, transparency, dieback, and the regrowth of foliage. This object-based approach summarizes the pixel data into mean crown indices assigned to crown objects which became the carrier of information. Models performed above expectations, with a significant weighted Cohen's kappa (κ>0.60 and p<0.001) using 70% of available data. Using in situ data for model development, crown condition was predicted forwards (2010) and backwards (2007) in time, capturing trends in crown condition and identifying decline in the healthiest between 2008 and 2010. The results confirm that combining spectral and textural information increased model sensitivity to small variations in crown condition. The methodology provides a cost-effective means for monitoring crown condition of this or other eucalypt species in native and plantation forests.

  4. 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...

  5. The use of Hall technique preformed metal crowns by specialist paediatric dentists in the UK

    OpenAIRE

    Roberts, A; McKay, A; Albadri, S

    2018-01-01

    Examines treatment planning involving Hall technique preformed metal crowns by specialists in paediatric dentistry. Explores clinical situations in which specialists in paediatric dentistry feel it is appropriate or not to fit Hall technique preformed metal crowns. Investigates which types of carious lesions are being treated with Hall technique preformed metal crowns by specialists in paediatric dentistry.

  6. 18-Crown-6 and Dibenzo-18-crown-6 Assisted Extraction of Cesium from Water into Room Temperature Ionic Liquids and Its Correlation with Stability Constants for Cesium Complexes

    Directory of Open Access Journals (Sweden)

    Igor Vladimirovich Pletnev

    2009-12-01

    Full Text Available The pH-profiles of the extraction of Cs+ into four conventional (1-butyl-3-methylimidazolium hexafluorophosphate and bis[trifluoromethylsulphonyl]imides of 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, and 1-(2-ethylhexyl-3- methylimidazolium and two novel (trioctylmethylammonium salicylate and tetrahexylammonium dihexylsulfosuccinate room temperature ionic liquids have been determined both in the absence and in the presence of crown ether (18-crown-6 or dibenzo-18-crown-6. The pH-profiles of distribution ratio of crown ethers have been established in the same conditions. The relationship of cesium extraction efficiency both with the stability of its complexes with crown ethers and crown ethers’ distribution ratio has been clarified.

  7. Synthesis, spectroscopic studies and inhibitory activity against bactria and fungi of acyclic and macrocyclic transition metal complexes containing a triamine coumarine Schiff base ligand

    Science.gov (United States)

    Abou-Hussein, A. A.; Linert, Wolfgang

    2015-04-01

    Two series of new mono and binuclear complexes with a Schiff base ligand derived from the condensation of 3-acetylcoumarine and diethylenetriamine, in the molar ratio 2:1 have been prepared. The ligand was characterized by elemental analysis, IR, UV-visible, 1H-NMR and mass spectra. The reaction of the Schiff base ligand with cobalt(II), nickel(II), copper(II), zinc(II) and oxovanadium(IV) lead to mono or binuclear species of cyclic or macrocyclic complexes, depending on the mole ratio of metal to ligand and as well as on the method of preparation. The Schiff base ligand behaves as a cyclic bidentate, tetradendate or pentaentadentae ligand. The formation of macrocyclic complexes depends significantly on the dimension of the internal cavity, the rigidity of the macrocycles, the nature of its donor atoms and on the complexing properties of the anion involved in the coordination. Electronic spectra and magnetic moments of the complexes indicate that the geometries of the metal centers are either square pyramidal or octahedral for acyclic or macro-cyclic complexes. The structures are consistent with the IR, UV-visible, ESR, 1H-NMR, mass spectra as well as conductivity and magnetic moment measurements. The Schiff base ligand and its metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi. Most of the complexes exhibit mild antibacterial and antifungal activities against these organisms.

  8. 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.

  9. Grafting of benzylic amide macrocycles onto acid-terminated self-assembled monolayers studied by XPS, RAIRS, and contact angle measurements

    NARCIS (Netherlands)

    Cecchet, F; Pilling, M; Hevesi, L; Schergna, S; Wong, JKY; Clarkson, GJ; Leigh, DA; Rudolf, P; Wong, Jenny K.Y.; Clarkson, Guy J.

    2003-01-01

    The grafting of benzylic amide macrocycles, the basic units of more complex mechanically interlocked architectures such as catenanes and rotaxanes, was performed via the functionalization of an acid-terminated self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA). Both chemical and

  10. 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…

  11. Base-induced self-assembly for one-dimensional coordination polymers via chiral pendant-armed Schiff base mononuclear Pb(II) macrocycles.

    Science.gov (United States)

    Zhang, Kun; Jin, Chao; Sun, Yuchen; Chang, Feifan; Huang, Wei

    2014-08-04

    A pair of 18-membered [1 + 1] chiral pendant-armed Schiff base macrocyclic mononuclear Pb(II) complexes with an unusual N1O2 coordination mode, synthesized from two chiral isomeric dialdehyde components, can be further self-assembled to one-dimensional ribbon coordination polymers by adding NaOH as a base to remove two phenolic protons.

  12. A novel complexity-to-diversity strategy for the diversity-oriented synthesis of structurally diverse and complex macrocycles from quinine.

    Science.gov (United States)

    Ciardiello, J J; Stewart, H L; Sore, H F; Galloway, W R J D; Spring, D R

    2017-06-01

    Recent years have witnessed a global decline in the productivity and advancement of the pharmaceutical industry. A major contributing factor to this is the downturn in drug discovery successes. This can be attributed to the lack of structural (particularly scaffold) diversity and structural complexity exhibited by current small molecule screening collections. Macrocycles have been shown to exhibit a diverse range of biological properties, with over 100 natural product-derived examples currently marketed as FDA-approved drugs. Despite this, synthetic macrocycles are widely considered to be a poorly explored structural class within drug discovery, which can be attributed to their synthetic intractability. Herein we describe a novel complexity-to-diversity strategy for the diversity-oriented synthesis of novel, structurally complex and diverse macrocyclic scaffolds from natural product starting materials. This approach exploits the inherent structural (including functional) and stereochemical complexity of natural products in order to rapidly generate diversity and complexity. Readily-accessible natural product-derived intermediates serve as structural templates which can be divergently functionalized with different building blocks to generate a diverse range of acyclic precursors. Subsequent macrocyclisation then furnishes compounds that are each based around a distinct molecular scaffold. Thus, high levels of library scaffold diversity can be rapidly achieved. In this proof-of-concept study, the natural product quinine was used as the foundation for library synthesis, and six novel structurally diverse, highly complex and functionalized macrocycles were generated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Reversible adaptation to photoinduced shape switching by oligomer-macrocycle interconversion with component selection in a three-state constitutional dynamic system.

    Science.gov (United States)

    Vantomme, Ghislaine; Lehn, Jean-Marie

    2014-12-01

    Light irradiation of the molecular photoswitch 1-E causes isomerization into the 1-Z configuration stabilized by an internal hydrogen bond. 1-E bears aldehyde groups allowing for dynamic covalent reaction with linear diamines. On photoinduced E/Z shape switching of 1 in presence of diamines, the system undergoes interconversion between two states, a non-cyclic oligomeric one and a macrocyclic one, corresponding respectively to the E and Z configurations of 1. With a mixture of linear α,ω-diamines, 1-E yields non-selective dynamic oligomers by random incorporation of diamine components. Photoswitching to the 1-Z form leads to constitutional adaptation with preferential formation of the macrocycle incorporating the best suited diamine, H2 N(CH2 )7 NH2 . In presence of metal cations, the E form switches from its unbound W shape to its coordinated U shape and yields the macrocycle resulting from the selective incorporation of the diamine H2 NCH2 CH2 OCH2 CH2 NH2 that contains an additional O coordination site. Taken together, the results obtained describe constitutional adaptation in a triple state system: an oligomeric one and two different macrocyclic ones generated in response to two orthogonal agents, a physical stimulus, light, or a chemical effector, metal cations. These three states present, towards the incorporation of diamine components, respectively no selection, photoselection and metalloselection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. Tensile bond strength of ceramic crowns to dentin using resin cements.

    Science.gov (United States)

    Simon, James F; de Rijk, Waldemar G; Hill, Jennifer; Hill, Nathaniel

    2011-01-01

    This study measured the bond strength of the self-adhesive resin cements and a bonded resin cement for crowns bonded to extracted teeth with preparations having a total taper greater than 30 degrees. A crown pull-off test was used with direction of pull along the path of insertion. The CAD/CAM system Cerec was used to create crowns with the pull-off loop as an integral part of the crown structure. One hundred extracted human molars were prepared for all-ceramic crowns with a 1.5-mm shoulder, greater than 30-degree axial wall convergence, a flat occlusal surface and 3 to 5 mm occlusal/ gingival height. All-ceramic crowns were cemented with five different self-adhesive cements (Rely X Unicem, Maxcem Elite, BisCem, SmartCem 2, and G-Cem) and one bonded resin cement (Multilink). Forfour cements (excluding GCem and Multilink) there were 2 groups, one with HF etching and one without ceramic surface treatment. The crowns were then subject to tensile stress until either the crown fractured or the crown was lifted off from the tooth. For several cements, the bond strength exceeded the tensile strength of the all-ceramic crown; thus, the crown fractured, leaving the cemented part of the crown on the tooth. The effect of ceramic surface etching was not statistically significant at p = 0.05; however, for each cement, the treated crowns showed a lower coefficient of variance (COV). For this study, the COV ranged from 24.9 % to 97.9 %. Loads ranged from 41.3 to 190.3 N. Some of the new self-etching resin cements can create bonds to non-retentive crown preparations that are stronger than the strength of a ceramic crown; however, these high bond strengths may not be able to be achieved consistently.

  19. Clinical Evaluation of Monolithic Zirconia Crowns: A Short-Term Pilot Report.

    Science.gov (United States)

    Kitaoka, Aki; Akatsuka, Ryo; Kato, Hiroaki; Yoda, Nobuhiro; Sasaki, Keiichi

    This study aimed to prospectively evaluate the clinical performance of monolithic zirconia crowns made of yttria-stabilized tetragonal zirconia polycrystal. A total of 26 crowns placed on premolar or molar teeth in 18 patients were evaluated at the time of crown placement and at 2 weeks, 6 months, 1 year, and 2 years after placement. Twenty-five crowns rated as satisfactory according to the California Dental Association quality evaluation system. Most of the abutment and antagonist teeth showed good periodontal condition. An enamel cracking occurred on one antagonist tooth 1 year after placement. Monolithic zirconia crowns can be a clinically acceptable prosthetic option.

  20. 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.

  1. Comparative fracture strength analysis of Lava and Digident CAD/CAM zirconia ceramic crowns

    OpenAIRE

    Kwon, Taek-Ka; Pak, Hyun-Soon; Yang, Jae-Ho; Han, Jung-Suk; Lee, Jai-Bong; Kim, Sung-Hun; Yeo, In-Sung

    2013-01-01

    PURPOSE All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. MATERIALS AND METHODS Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also ...

  2. Clinical evaluation of and parental satisfaction with resin-faced stainless steel crowns.

    Science.gov (United States)

    Roberts, C; Lee, J Y; Wright, J T

    2001-01-01

    This study evaluated the clinical success and parental acceptance of anterior primary dentition caries treatment with prefabricated resin-faced stainless steel crowns. A retrospective analysis of maxillary anterior primary dentition caries treatment using Whiter Biter II Crowns was performed. Each crown was evaluated for retention, fracture, interface failure, color match, marginal integrity, and surface texture. Parental satisfaction regarding the esthetics of the crowns was evaluated by survey. Thirty-eight crowns were evaluated in 12 children. The average crown age at time of examination was 20.7 months. Three teeth were lost to trauma with all other crowns remaining intact. Twelve crowns (32%) showed loss of at least some facial resin. Nine crowns (24%) had complete loss of the resin facing. Overall parental satisfaction with the treatment was excellent, however, satisfaction with crown esthetics received the lowest rating. While parental satisfaction with treatment of anterior primary dentition caries with prefabricated resin-faced stainless steel crowns is excellent, the high failure rate of the resin facings is problematic.

  3. Effect of water temperature on the fit of provisional crown margins during polymerization.

    Science.gov (United States)

    Ogawa, T; Aizawa, S; Tanaka, M; Matsuya, S; Hasegawa, A; Koyano, K

    1999-12-01

    When fabricating a provisional crown with the direct technique, dentists are concerned with margin discrepancies that result from polymerization shrinkage. This in vitro study examined the effect of water temperature on the fit of provisional crown margins during resin polymerization. The experiment was designed to simulate a direct technique to fabricate provisional crowns. After mixing autopolymerizing methyl methacrylate resin, the material was placed in a preformed polycarbonate crown. The crown was seated on a prepared premolar-shaped die with a shoulder margin. After 1 minute and 50 seconds, the crown was removed and polymerization was continued under the following conditions: 20 degrees C air, and water at 0 degrees C, 10 degrees C, 20 degrees C, 30 degrees C, 40 degrees C, 60 degrees C, and 80 degrees C. Six minutes after polymerization, the crown was trimmed and reseated on the die. Discrepancy of crown margin was measured with a 3-dimensional digitizer. Margin discrepancy varied with the condition during resin-polymerization (ANOVA, P crowns polymerized in 20 degrees C and 30 degrees C water revealed the best margin fit, showing 3 times more accurate margin fit than those polymerized in 20 degrees C air (Bonferroni/Dunn procedure, P provisional crowns using the direct technique. Water temperatures of 20 degrees C and 30 degrees C produced the best fit at the margin of the provisional crown.

  4. 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.

  5. 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.

  6. Mononuclear and binuclear lanthanide complexes of the macrocyclic polyamine polycarboxylic ligands H8OTEC and H8OHEC

    International Nuclear Information System (INIS)

    Schumann, H.; Boettger, U.; Zschunke, A; Weisshoff, H.

    1998-01-01

    Full text: In recent years there is a growing interest in design and synthesis of macrocyclic ligands and of their dinuclear complexes, owing to their relevance in basic and applied chemistry.1 Our studies are aimed to synthesize ligands based on the DOTA or DTPA backbone which can at least bind two trivalent lanthanide ions, to study their stereochemical properties and to determine the stability of such complexes in aqueous solution. We have recently reported the successful synthesis and characterization of two new hexadecadentate macrocyclic polyaza polycarboxylate ligands OTEC (1,4,7,10,13,16,19,22 - octaazacyclotetracosane - 1,4,7,10,13,16,19,22-octaacetic acid) and OHEC (1,4,7,10,14,17,20,-23 - octaazacyclohexacosane - 1,4,7,10,14,17,20,23 - octaacetic acid) and some of their mono- and dinuclear lanthanide(III) chelate complexes which are highly stable and watersoluble. The acid-base properties of these ligands were characterized by using potentiometry and NMR titration techniques. The determination of the thermodynamic stability constants governing the formation of the complexes with Ca(II), Mg(II) and Gd(III) are in progress. The solid structure of four homodinuclear lanthanide(III)chelates (La(III), Eu(III), Gd(III) and Y(III)) of the ligand OHEC was investigated by X-ray crystal structure analysis. In the isostructural complexes the lanthanide ions are nine coordinated by eight donors provided by the ligand and one oxygen of a water molecule. This results in an unusual coordination polyhedron different from that found in the lanthanide complexes of the ligand DOTA and TETA. The conformation of the macrocycles in these complexes was compared to those of the parent compound 1,4,7,10,14,17,20,23-octaazacyclohex-acosane and its dinuclear copper complex. Due to NMR investigations the environment of the lanthanide cation is probably identical in solution and in the solid state. There is nearly a quantitative fit between the crystal structure and the major

  7. 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)

  8. 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)

  9. 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.

  10. Modeling Tree Crown Dynamics with 3D Partial Differential Equations

    Directory of Open Access Journals (Sweden)

    Robert eBeyer

    2014-07-01

    Full Text Available 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 towards 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.

  11. 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.

  12. 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

  13. Theobrominium perchlorate dibenzo-18-crown-6 3.25-hydrate

    Directory of Open Access Journals (Sweden)

    Vladislav Kulikov

    2013-07-01

    Full Text Available The co-crystal, C7H9N4O2+·ClO4−·C20H24O6·3.25H2O, consists of theobrominium (3,7-dimethyl-2,6-dioxo-1H-purin-9-ium cations, perchlorate anions and dibenzo-18-crown-6 and water molecules. The crown ether is in a bent conformation, in which the planes of the aromatic rings subtend an angle of 63.7 (1°. Intermolecular O—H...O hydrogen bonding between the water molecules and the O atoms of the cyclic ether delimit an empty space reminiscent of a hollow cage. The water molecules are additionally linked to the cations by N—H...O hydrogen bonding. One of the positions of the water molecules is occupied only fractionally (25% and is located outside this framework.

  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. 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

  16. [Fracture toughness of zirconia ceramic crowns made by feather-edge tooth preparation design].

    Science.gov (United States)

    Mirković, Nemanja; Gostović, Aleksandra Spadijer; Lazić, Zoran; Trifković, Branka

    2012-07-01

    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. 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 mmn 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. 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 2000 N, what was double beyond a recommended value. The mean value of fracture toughness in the feather-edge group was 2090 N, and in shoulder group it was 2214 N. 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 gingival inflammatory response.

  17. 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....

  18. 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...

  19. 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 (Pcrowns 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 (Pcrowns at the facial surface and with the horizontal marginal discrepancies of the Caulk interim crowns at the lingual surface (Pcrowns fabricated by CAD/CAM as compared with PMMA crowns; however, this difference was not observed for the horizontal component. The percentage dye penetration was correlated with vertical and horizontal

  20. Reliability of metalloceramic and zirconia-based ceramic crowns.

    Science.gov (United States)

    Silva, N R F A; Bonfante, E A; Zavanelli, R A; Thompson, V P; Ferencz, J L; Coelho, P G

    2010-10-01

    Despite the increasing utilization of all-ceramic crown systems, their mechanical performance relative to that of metal ceramic restorations (MCR) has yet to be determined. This investigation tested the hypothesis that MCR present higher reliability over two Y-TZP all-ceramic crown systems under mouth-motion fatigue conditions. A CAD-based tooth preparation with the average dimensions of a mandibular first molar was used as a master die to fabricate all restorations. One 0.5-mm Pd-Ag and two Y-TZP system cores were veneered with 1.5 mm porcelain. Crowns were cemented onto aged (60 days in water) composite (Z100, 3M/ESPE) reproductions of the die. Mouth-motion fatigue was performed, and use level probability Weibull curves were determined. Failure modes of all systems included chipping or fracture of the porcelain veneer initiating at the indentation site. Fatigue was an acceleration factor for all-ceramic systems, but not for the MCR system. The latter presented significantly higher reliability under mouth-motion cyclic mechanical testing.

  1. Reliability of Metalloceramic and Zirconia-based Ceramic Crowns

    Science.gov (United States)

    Silva, N.R.F.A.; Bonfante, E.A.; Zavanelli, R.A.; Thompson, V.P.; Ferencz, J.L.; Coelho, P.G.

    2010-01-01

    Despite the increasing utilization of all-ceramic crown systems, their mechanical performance relative to that of metal ceramic restorations (MCR) has yet to be determined. This investigation tested the hypothesis that MCR present higher reliability over two Y-TZP all-ceramic crown systems under mouth-motion fatigue conditions. A CAD-based tooth preparation with the average dimensions of a mandibular first molar was used as a master die to fabricate all restorations. One 0.5-mm Pd-Ag and two Y-TZP system cores were veneered with 1.5 mm porcelain. Crowns were cemented onto aged (60 days in water) composite (Z100, 3M/ESPE) reproductions of the die. Mouth-motion fatigue was performed, and use level probability Weibull curves were determined. Failure modes of all systems included chipping or fracture of the porcelain veneer initiating at the indentation site. Fatigue was an acceleration factor for all-ceramic systems, but not for the MCR system. The latter presented significantly higher reliability under mouth-motion cyclic mechanical testing. PMID:20660796

  2. 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

  3. Assessment of nickel release from stainless steel crowns.

    Directory of Open Access Journals (Sweden)

    Nahid Ramazani

    2014-06-01

    Full Text Available Adverse effects of dental materials, especially metals, have been an important issue in recent decades.The purpose of this study was to determine the amount of nickel released from stainless steel crowns in artificial saliva.In this in-vitro study, 270 stainless steel crowns were divided into five groups, each with nine subgroups. Each group (I to V was comprised of four, five, six, seven and eight crowns, respectively. Each subgroup was placed in a polyethylene jar containing artificial saliva and held in an incubator at 37°C for four weeks. The amount of released nickel was determined on days 1, 7, 14, 21 and 28, using an atomic absorption spectrophotometer. Wilcoxon Signed-Rank and Kruskal-Wallis with Dunn's post hoc tests (SPSS software, v. 18 were used for statistical analysis at a significance level of 0.05.The mean level of nickel on day 1 was more than that of day 7; this difference was statistically significant for all groups (P < 0.05, except for group II (P = 0.086. Also, the mean difference of released nickel between the groups was significant on day 1 (P = 0.006 and was insignificant on day 7 (P = 0.620. The nickel levels were zero on days 14, 21, and 28.The amount of nickel was below the toxic level and did not exceed the dietary intake.

  4. 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.

  5. Dental ceramics and the molar crown testing ground

    Directory of Open Access Journals (Sweden)

    Van P. Thompson

    2004-01-01

    Full Text Available All ceramic crowns are highly esthetic restorations and their popularity has risen with the demand for life-like and cosmetic dentistry. Recent ceramic research has concentrated on developing a fundamental understanding of ceramic damage modes as influenced by microstructure. Dental investigations have elucidated three damage modes for ceramic layers in the 0.5-2 mm thickness using point contacts that duplicate tooth cuspal radii; classic Hertzian cone cracking, yield (pseudo-plastic behavior, and flexural cracking. Constitutive equations based upon materials properties have been developed that predict the damage modes operational for a given ceramic and thickness. Ceramic thickness or thickness of the stiff supporting core in layer crowns is critical in flexural cracking as well as the flaw state of the inner aspect of the crown. The elastic module of the supporting structure and of the luting cement and its thickness play a role in flexural fracture. Clinical studies of ceramics extending over 16 years are compared to the above relationships and predictions. Recommendations for clinical practice are made based upon the above.

  6. Immediate maxillary lateral incisor implants with nonocclusal loading provisional crowns.

    Science.gov (United States)

    Peñarrocha, Miguel; Lamas, Joana; Peñarrocha, Maria; Garcia, Berta

    2008-01-01

    This clinical report series describes a treatment modality involving immediately placed dental implants in maxillary lateral incisor sites using noncemented immediate provisional crowns retained with calcinable copings (prosthetic complement used in preparing the metal for the definitive prosthesis). Ten implants were placed in eight patients for the replacement of maxillary lateral incisors: two immediate and eight corresponding to cases of agenesis. All were subjected to immediate rehabilitation with provisional acrylic resin crowns in nonocclusal loading. One implant failed 3 weeks after placement due to acute local trauma. The other nine remained functional within the mouth, with normal clinical and radiological characteristics after a minimum of 12-month follow-up. Immediate placement of implant fixed provisional restorations retained by friction in maxillary lateral incisors offers an esthetic solution, eliminates the need for a removable provisional restoration, and avoids implant failures associated with excess cement or screw loosening. Moreover, in the case of extractions, immediate placement and provisionalization of implants in maxillary lateral incisors can effectively optimize the peri-implant esthetic results by maintaining the existing hard and soft tissue architecture of the replaced tooth. As no cement or screws are required, and the provisional crowns are placed in nonocclusal loading, the risk of complications is minimized.

  7. In vitro study of fracture strength of provisional crown materials.

    Science.gov (United States)

    Karaokutan, Isil; Sayin, Gulsum; Kara, Ozlem

    2015-02-01

    The purpose of this report was to evaluate the effect of the fabrication method and material type on the fracture strength of provisional crowns. A master model with one crown (maxillary left second premolar) was manufactured from Cr-Co alloy. The master model was scanned, and the data set was transferred to a CAD/CAM unit (Yenamak D50, Yenadent Ltd, Istanbul, Turkey) for the Cercon Base group. For the other groups, temporary crowns were produced by direct fabrication methods (Imident, Temdent, Structur Premium, Takilon, Systemp c&b II, and Acrytemp). The specimens were subjected to water storage at 37℃ for 24 hours, and then they were thermocycled (TC, 5000×, 5-55℃) (n=10). The maximum force at fracture (Fmax) was measured in a universal test machine at 1 mm/min. Data was analyzed by non-parametric statistics (α=.05). Fmax values varied between 711.09-1392.1 N. In the PMMA groups, Takilon showed the lowest values (711.09 N), and Cercon Base showed the highest values (959.59 N). In the composite groups, Structur Premium showed the highest values (1392.1 N), and Acrytemp showed the lowest values (910.05 N). The composite groups showed significantly higher values than the PMMA groups (P=.01). Composite-based materials showed significantly higher fracture strengths than PMMA-based materials. The CAD-CAM technique offers more advantages than the direct technique.

  8. 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...

  9. 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.

  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. In vitro microleakage of luting cements and crown foundation material.

    Science.gov (United States)

    Lindquist, T J; Connolly, J

    2001-03-01

    Microleakage is a concern for the long-term prognosis of a cemented crown and foundation. The aims of this investigation were, first, to evaluate microleakage of zinc phosphate cement and resin-reinforced glass ionomer cement under ideal (dry) versus contaminated (wet) conditions, and second, to compare 3 foundations under both ideal and contaminated conditions. One hundred forty extracted molar teeth were cleaned and mounted. Tooth preparations for complete veneer cast crowns were completed with a chamfer finish line. A mesial surface class II cavity preparation 4 mm wide buccolingually and 2 mm deep was made in each tooth. Seven restorative groups were formed: amalgam/cavity varnish, amalgam/dentinal bonding agent, and composite/dentinal bonding agent, each with dry and contaminated groups, and a seventh group of class II cavity preparations without foundations. Finish lines for crown margins were refined 1.5 mm gingival to the restoration. Artificial crowns were cast in type III gold. Treatment groups were divided into 4 cement groups: dry and contaminated zinc phosphate cement and dry and contaminated resin-reinforced glass ionomer cement. The specimens were thermocycled and immersed in erythrosine B solution for 24 hours. Subsequently, they were rinsed, and their coronal portions were embedded in clear resin. Teeth were sectioned mesiodistally, and standard photomicrographs were made. The microleakage of each restoration and crown was measured. The least foundation microleakage was recorded for amalgam/dentinal bonding agents (ideal group) and composite/dentinal bonding agents (ideal group). The most microleakage was observed within the group without a foundation. In cement groups, the control and experiment sides were evaluated separately but displayed the same order of finding. The least leakage was recorded with resin-reinforced glass ionomer cement (ideal group); the most microleakage was noted with zinc phosphate cement (ideal group). An interaction was

  12. 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

  13. 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

    2012-05-01

    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

  14. 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

  15. Synthesis, characterization, nano-sized binuclear nickel complexes, DFT calculations and antibacterial evaluation of new macrocyclic Schiff base compounds

    Science.gov (United States)

    Parsaee, Zohreh; Mohammadi, Khosro

    2017-06-01

    Some new macrocyclic bridged dianilines tetradentate with N4coordination sphere Schiff base ligands and their nickel(II)complexes with general formula [{Ni2LCl4} where L = (C20H14N2X)2, X = SO2, O, CH2] have been synthesized. The compounds have been characterized by FT-IR, 1H and 13C NMR, mass spectroscopy, TGA, elemental analysis, molar conductivity and magnetic moment techniques. Scanning electron microscopy (SEM) shows nano-sized structures under 100 nm for nickel (II) complexes. NiO nanoparticle was achieved via the thermal decomposition method and analyzed by FT-IR, SEM and X-ray powder diffraction which indicates closeaccordance to standard pattern of NiO nanoparticle. All the Schiff bases and their complexes have been detected in vitro both for antibacterial activity against two gram-negative and two gram-positive bacteria. The nickel(II) complexes were found to be more active than the free macrocycle Schiff bases. In addition, computational studies of three ligands have been carried out at the DFT-B3LYP/6-31G+(d,p) level of theory on the spectroscopic properties, including IR, 1HNMR and 13CNMR spectroscopy. The correlation between the theoretical and the experimental vibrational frequencies, 1H NMR and 13C NMR of the ligands were 0.999, 0.930-0.973 and 0.917-0.995, respectively. Also, the energy gap was determined and by using HOMO and LUMO energy values, chemical hardness-softness, electronegativity and electrophilic index were calculated.

  16. Adaptation of a 96-well plate larval migration inhibition test for measuring the sensitivity of cyathostomins to macrocyclic lactone anthelmintics.

    Science.gov (United States)

    Beasley, A M; Coleman, G T; Kotze, A C

    2017-10-15

    The use of macrocyclic lactone drugs for control of equine cyathostomins is threatened by increasing levels of resistance. Detection of changes in drug sensitivity is important for effective and sustainable management of cyathostomins, however, at present such detection relies on the use of the faecal egg count reduction test, which is known to be an insensitive method. The present study therefore aimed to examine the use of a 96-well plate larval migration inhibition test for detection of resistance to macrocyclic lactone drugs in cyathostomins. We optimised conditions for migration of larvae, and examined the effects of larval storage time on drug dose responses. The modified test was able to define the sensitivity of cyathostomin isolates to ivermectin and eprinomectin in terms of dose response curves, and IC 50 and IC 95 values. The IC 95 showed much greater consistency than the IC 50 with larvae that had been stored for different periods prior to the test. Comparisons between two isolates, which had both been defined previously as susceptible using faecal egg count reduction tests, showed more variation at the IC 50 compared to the IC 95 . Limitations of the test included the degree of variation in control-well migration despite optimisation of migration incubation conditions, and the need to incorporate a method to determine the species composition of the larval populations to account for possible species differences in drug sensitivity among cyathostomins. Validation of the technique on reference susceptible and resistant isolates of known species composition is still required. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. 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...... as controls. Paired sample t-testand Pearson´s correlation analysis were used to analyze implant position, dimension of crownand papilla fill.Cohen’s ¿ andSpearman correlation were used to validate the PIS.The implant-supported crown was statistically longer than the contra-lateral tooth......, and there was significant correlation between the oro-facial position of the implant and the crown length difference (r=.607, p=.001). The distalpapilla was significantly shorter than the mesialpapilla at implant-supported crowns (ptooth (p=.415...

  18. Twenty-year follow-up of metal-ceramic single crowns: a retrospective study.

    Science.gov (United States)

    Näpänkangas, Ritva; Raustia, Aune

    2008-01-01

    The aim of this clinical retrospective study was to evaluate the survival and success of single metal-ceramic crowns after 20 years. The biologic and technical complications as well as patient satisfaction were recorded. Fifty patients treated with 100 single metal-ceramic crowns attended the clinical 20-year follow-up examination. The mean follow-up time was 18.8 years (17.5 to 20.5 years). Twenty-one teeth with single crowns were extracted because of root fractures or esthetic or periodontal reasons. Ninety-seven percent of the subjects had no complaints about the esthetics of the crowns. The most common clinical findings were supragingival crown margins caused by gingival recessions, gingival bleeding on probing, and occlusal wear in opposing teeth. The success of the crowns after 20 years was 75%, and the survival was 78%. In the 20-year follow-up of single metal-ceramic crowns, there were few biologic and technical complications, and patients were satisfied with the crowns. Crown removal was in most cases the result of root fractures in single crowns with endodontic posts.

  19. Simulation of clinical fractures for three different all-ceramic crowns

    Science.gov (United States)

    Øilo, Marit; Kvam, Ketil; Gjerdet, Nils R

    2014-01-01

    Comparison of fracture strength and fracture modes of different all-ceramic crown systems is not straightforward. Established methods for reliable testing of all-ceramic crowns are not currently available. Published in-vitro tests rarely simulate clinical failure modes and are therefore unsuited to distinguish between the materials. The in-vivo trials usually lack assessment of failure modes. Fractographic analyses show that clinical crowns usually fail from cracks initiating in the cervical margins, whereas in-vitro specimens fail from contact damage at the occlusal loading point. The aim of this study was to compare three all-ceramic systems using a clinically relevant test method that is able to simulate clinical failure modes. Ten incisor crowns of three types of all-ceramic systems were exposed to soft loading until fracture. The initiation and propagation of cracks in these crowns were compared with those of a reference group of crowns that failed during clinical use. All crowns fractured in a manner similar to fracture of the clinical reference crowns. The zirconia crowns fractured at statistically significantly higher loads than alumina and glass-ceramic crowns. Fracture initiation was in the core material, cervically in the approximal areas. PMID:24698209

  20. Shear bond strength of self-ligating orthodontic brackets on different types of porcelain crowns

    Directory of Open Access Journals (Sweden)

    Karamdeep Singh Ahluwalia

    2013-01-01

    Full Text Available Aim: The aim of this study is to compare shear bond strength (SBS and adhesive remnant index (ARI of self-ligating orthodontic brackets bonded to different porcelain crowns. Materials and Methods: Three groups of different types of porcelain crowns, each containing 12 crowns were fabricated by the same technician and allocated to one of the study groups as follows: Group I - IPS porcelain crowns (Ivoclar Vivadent AG, Schaan, Liechtenstein, Group II - Porcelain fused to zirconia crowns (Zirkonzahn GmbH, Gais, Italy, Noritake Co., Tokyo, Japan and Group III - Conventional porcelain fused to metal crowns (Ceramco3, Densply, PA, USA. The orthodontic brackets were bonded to these crowns using hydrofluoric acid (HFA + silane etching protocol. After bonding, the SBS of the brackets were tested with a universal testing machine under standard test conditions. Results: Statistical evaluation using analysis of variance showed a significant difference between the groups (P 0.05. Chi-square comparison revealed no significant difference in ARI scores between groups (P > 0.05. Conclusions: When HFA + silane etching protocol were used, IPS crowns showed the greatest SBS of orthodontic brackets. The ARI score was non-significant. Therefore, if there is a need to place crowns over teeth then these crowns can be used for restoration of teeth before orthodontic treatment.

  1. Strength of CAD/CAM-generated esthetic ceramic molar implant crowns.

    Science.gov (United States)

    Wolf, Daniel; Bindl, Andreas; Schmidlin, Patrick R; Lüthy, Heinz; Mörmann, Werner H

    2008-01-01

    One-visit in-office CAD/CAM fabrication of esthetic ceramic crowns as a superstructure for posterior implants is quite new. The aim of the study was to evaluate the strength of esthetic ceramic CAD/CAM crowns with varied occlusal thickness and seated with adhesive and nonadhesive cements on titanium and zirconia abutments. Esthetic ceramic CAD/CAM-generated molar crowns (n = 15 per group) with occlusal thicknesses of 0.5 mm and 1.5 mm were seated on titanium (1) and zirconia (2) abutments: noncemented (a) and with nonadhesive cement (b) or 2 adhesive resin-based cements (c) and (d). In addition, 15 molar crowns with 5.5-mm occlusal thickness were seated on short zirconia abutments (3) using cements (c) and (d). All crowns had the identical occlusal morphology and were loaded with a crosshead speed of 0.5 mm/min until fracture. Load data were analyzed using 2-way ANOVA, the Scheffé test, and Weibull probability of failure analysis. Fracture loads of 1.5-mm occlusal thickness crowns (a, b, c, d) were higher (P crowns (except for group ld). Occlusal 5.5-mm crowns on short zirconia abutments had similar (2c) or less (2d) strength than the respective 1.5-mm crowns. Nonadhesive crowns (1b, 2b) were weaker (P crowns (1c, 1d, 2c, 2d). Fracture loads of 0.5- and 1.5-mm crowns were significantly higher on titanium than on zirconia abutments with both cements. Adhesive cement d generally showed higher fracture loads than c on both titanium and zirconia. Esthetic ceramic CAD/CAM molar implant crowns gained high strength with adhesive cements on both titanium and zirconia implant abutments compared to nonadhesive cementation.

  2. Evaluation of marginal circumference and marginal thickness changes in precrimped stainless steel crowns, after recrimping

    Directory of Open Access Journals (Sweden)

    Afshar H

    2006-07-01

    Full Text Available Background and Aim: The need for recrimping precrimped stainless steel crowns by the dentist in clinic is controversial. This study aimed to evaluate the rate of marginal circumference and marginal thickness change of precrimped stainless steel crowns after recrimping. Materials and Methods: In this experimental study, 30 primary photos were taken from margins of 30 S.S.Cs (3M, Ni-Cr related to tooth 85 with a digital camera fixed at a determined distance. Margins of crowns were crimped by 114 and 137 pliers with a controlled force (0.2 N and then 30 secondary photos were taken in the same conditions. The circumference of crown margins in primary (group A and secondary (group B photos were assessed by a digitizer system. Comparing the circumferences of crown margins in primary and secondary photos showed a significant decrease after crimping. Thickness of 30 random points on the crown margins of a crown similar to mentioned cases was measured by SEM (×150. Then similar procedures including taking a primary photo, crimping and taking a secondary photo was done for the sample crown. After significant reduction in margin circumference, thickness of 30 other random points on the crown margin were measured by SEM. Data were analyzed by paired sample t-test with p<0.05 as the limit of significance. Results: The mean marginal circumference of precrimped stainless steel crowns was reduced by 7.3% which was significant (P<0.001. On the other hand the mean marginal thickness of sample stainless steel crown showed 18µ increase. Conclusion: According to the results of this study, marginal circumference of precrimped stainless steel crowns (3M, Ni-Cr showed a significant decrease after crimping. It is concluded that crimping the stainless steel crowns even for precrimped ones seems necessary.

  3. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc01507c Click here for additional data file.

    Science.gov (United States)

    Mangold, Shane L.

    2015-01-01

    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E- and Z-olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E- or Z-olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM. PMID:26509000

  4. Fracture Resistance of Monolithic High Translucency Zirconia Implant-Supported Crowns.

    Science.gov (United States)

    Brizuela-Velasco, Aritza; Diéguez-Pereira, Markel; Álvarez-Arenal, Ángel; Chávarri-Prado, David; Solaberrieta, Eneko; Fernández-González, Felipe J; Chento-Valiente, Yelko; Santamaría-Arrieta, Gorka

    2016-10-01

    To evaluate the resistance to axial forces of screw-retained monolithic high translucency zirconia (mHTZr) crowns compared with high translucency zirconia + feldspathic ceramic (HTZrC) crowns, low translucency zirconia + feldspathic ceramic (LTZrC) crowns, and metal-ceramic (MC) crowns, and also to observe the different fracture patterns between all groups. Twenty-four crowns were fabricated (6 of each group) and loaded until failure, using a testing machine with a 5.0-kN load cell. Mean fracture results varied between 1092.7 N (LTZrC group) and 3439.7 N (mHTZr group). No statistically significant differences were found between the HTZrC, LTZrC, and MC groups. However, statistically significant differences (P zirconia implant-supported crowns proved to be the toughest group studied when an axial force was applied. Fracture patterns varied between different materials, chipping being the most common occurrence.

  5. [Clinical evaluation of the zirconia all ceramic crowns in 40 consecutive patients].

    Science.gov (United States)

    Qi, Bing; He, Yan

    2016-06-01

    To investigate clinical application, aesthetics, stability and bio-compatibility of zirconia all-ceramic crowns in prosthodontic patients. Computer aided design and manufacturing techniques were used to make zirconia all ceramic crowns in 40 patients. They were divided into 2 groups according to the thickness of the gingival thickness. After 12 months of clinical observation, the aesthetics, stability, and bio-compatibility were evaluated by the crown color, crown edge fitness, losing ratio and gingival health. The data were analyzed using SPSS 13.0 software package. Slight marginal discrepancy was observed in 2 zirconia all ceramic crowns, no evidence of decay was observed at 1 year. Zirconia all ceramic crowns have a low fracture rate, good biological properties and excellent esthetic properties. It is ideal esthetic prosthesis.

  6. Holographic evaluation of the marginal fits of complete crowns loaded at the central fossa

    Science.gov (United States)

    Chen, Terry Y.; Chang, Guan L.; Wu, Shih H.

    1995-05-01

    In dentistry, a defect of cementation on the margins of crowns accumulates bacterial plaque easily. This can result in recurrent caries and periodontal disease. In this paper holographic interferometry was applied to evaluate the effect of masticatory force on various complete crowns. Four complete molar crowns made from different materials (Au alloy, Pd-Ag alloy, Ni-Cr alloy, and porcelain fused to metal) were tested. The out-of-plane displacements of the crown specimens were measured by the method of multiple observations. The displacements measured range from 6 to 10 micrometers under normal load (25 N). However, the marginal openings of all four crowns were estimated to be less than 0.2 micrometers . In addition the defect of the crown was examined.

  7. Holographic evaluation of the marginal fit of complete crowns loaded at central fossa

    Science.gov (United States)

    Chen, Terry Y.; Chang, Guan L.; Wu, Shih H.

    1993-07-01

    In dentistry, the defect of cementation on the margins of crowns accumulates bacterial plaque easily. This can result in recurrent caries and periodontal disease. In this paper holographic interferometry is applied to study the effect of masticatory force on various complete crowns. Four complete molar crowns made from different casting materials (Au, Pd-Ag, Ni-Cr, and PFM) were tested. The horizontal displacements of two points near the margin, measured by the method of multiple observations, could be as large as 15 micrometers under normal load (25 kgw). However, the marginal discrepancy of all four crowns estimated were quite small (cementation between the crown and the tooth is quite good. Nevertheless, when the load was increased to 45 kgw, a defect of cementation was found on the Pd-Ag crown.

  8. MOLECULAR CLIPS BASED ON THE CROWN ETHERS: PROSPECTIVE RECEPTORS FOR THE Sr2+CATIONS REMOVAL

    Directory of Open Access Journals (Sweden)

    A. Yu. Lyapunov

    2015-04-01

    Full Text Available Strontium cation complexation with diphenylglycoluril-based molecular clips containing 12-crown-4, 15-crown-5, 18-crown-6 and 21-crown-7 residues was qualitatively studied by FAB mass-spectrometry. It was found that at low concentrations of Sr2+ cations molecular clip with fragments of 15-crown-5 is the most effective, and it is assumed that it is due to the formation of the most stable «sandwich-type» complex. The higher removal degree with an excess of Sr2+ cations is observed in the case of molecular clips with fragments of 18-crown-6 due to the formation of 1:2 composition complexes.

  9. Fracture Resistance of Non-Metallic Molar Crowns Manufactured with CEREC 3D

    Science.gov (United States)

    Madani, Dalia A.

    Objectives. To compare fracture strength and fatigue resistance of ceramic (ProCAD, Ivoclar-Vivadent) (C) and resin composite (Paradigm MZ100, 3M/ ESPE) (R) crowns made with CEREC-3D. Methods. A prepared ivorine molar tooth was duplicated to produce 40 identical prepared specimens made of epoxy resin (Viade). Twenty (C) crowns and 20 (R) were cemented to their dies using resin cement. Ten of each group were subjected to compressive loading to fracture. The remaining 10 of each group were subjected to mechanical cyclic loading for 500,000 cycles. The survivors were subjected to compressive loading to fracture. Results. No significant difference in mean fracture load was found between the two materials. However, only 30% of the (C) crowns vs. 100% of the (R) crowns survived the cyclic loading test. Conclusions. (R) crowns demonstrated higher fatigue Resistance than (C) crowns in-vitro and might better resist cracking in-vivo.

  10. 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.

  11. Determining the Degree of Anthelmintic Resistance against Macrocyclic Lactones in Small Strongylus, Based on the Larvae Development Analysis (LDA in Horses from Grasslands in the Department of Casanare

    Directory of Open Access Journals (Sweden)

    Germán Alonso Prada

    2011-06-01

    Full Text Available This study was conducted in the grasslands of the Department of Casanare, seeking to determine the degree of anthelmintic susceptibility or resistance against macrocyclic lactones in small populations of Strongylus in this region of the country. Samples were taken from four municipalities in the department: Aguazul, Paz de Ariporo, Maní and El Yopal, between June, 2006 and April, 2007, where ten fresh fecal samples were collected in each municipality, directly from the field and in a completely random way. The samples were processed using the MacMaster coprological technique, thus determining the highest count of fecal epg by municipality. L3 larvae were extracted from each of the six samples with the highest count of fecal epg through the coprological and Baermann-Wetzel tests with which the Larvae Development Analysis (LDA test was run, detecting Small Strongylus highly susceptible to the action of macrocyclic lactones (ivermectin.

  12. 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.

  13. Unicuspid and bicuspid tooth crown formation in squamates.

    Science.gov (United States)

    Handrigan, Gregory R; Richman, Joy M

    2011-12-15

    The molecular and developmental factors that regulate tooth morphogenesis in nonmammalian species, such as snakes and lizards, have received relatively little attention compared to mammals. Here we describe the development of unicuspid and bicuspid teeth in squamate species. The simple, cone-shaped tooth crown of the bearded dragon and ball python is established at cap stage and fixed in shape by the differentiation of cells and the secretion of dental matrices. Enamel production, as demonstrated by amelogenin expression, occurs relatively earlier in squamate teeth than in mouse molars. We suggest that the early differentiation in squamate unicuspid teeth at cap stage correlates with a more rudimentary tooth crown shape. The leopard gecko can form a bicuspid tooth crown despite the early onset of differentiation. Cusp formation in the gecko does not occur by the folding of the inner enamel epithelium, as in the mouse molar, but by the differential secretion of enamel. Ameloblasts forming the enamel epithelial bulge, a central swelling of cells in the inner enamel epithelium, secrete amelogenin at cap stage, but cease to do so by bell stage. Meanwhile, other ameloblasts in the inner enamel epithelium continue to secrete enamel, forming cusp tips on either side of the bulge. Bulge cells specifically express the gene Bmp2, which we suggest serves as a pro-differentiation signal for cells of the gecko enamel organ. In this regard, the enamel epithelial bulge of the gecko may be more functionally analogous to the secondary enamel knot of mammals than the primary enamel knot. Copyright © 2011 Wiley Periodicals, Inc., A Wiley Company.

  14. Crown retention and flexural strength of eight provisional cements.

    Science.gov (United States)

    Lawson, Nathaniel C; Burgess, John O; Mercante, Donald

    2007-12-01

    Few studies have compared the retention of resin-based and zinc-oxide noneugenol provisional cements. Crown retention testing is difficult and variable; therefore, a simpler method of testing by using flexural strength is indicated. The purpose of this study was to measure the retention of base metal alloy castings to dentin provided by 8 provisional cements (3 resin-based and 5 zinc oxide) and correlate the retention to their flexural strength. Flexural strength specimens (2.5 x 2.5 x 22 mm) were made of each cement. The specimens were placed in a 3-point bending testing mode and loaded at 1 mm/min until failure. Ten extracted teeth were milled to a standardized complete crown preparation, fitted with Rexillium III castings, and cemented with each provisional cement. The specimens were subjected to a tensile load (1 mm/min) until failure in a universal testing machine. The flexural strength for each cement was calculated in MPa and correlated to the retention. A 1-way ANOVA and Tukey HSD post hoc analysis were used to determine significant intergroup differences (alpha=.05). Linear regression was used to correlate flexural strength and crown retention (alpha=.05). Significant differences were found in the flexural strengths and retention provided by the various cements. Flexure strength was correlated with cement retention for resin-based cements (r=0.998) but not zinc-oxide noneugenol cements (r=0.058). Based on a 20-degree preparation, stronger cements provide increased retention. Therefore, the desired amount of retention should be based on both the cement and a clinical evaluation of the preparation.

  15. Crown dimensions and proximal enamel thickness of mandibular second bicuspids

    Directory of Open Access Journals (Sweden)

    Sérgio Augusto Fernandes

    2011-08-01

    Full Text Available To achieve proper recontouring of anterior and posterior teeth, to obtain optimal morphology during enamel stripping, it is important to be aware of dental anatomy. This study aimed at evaluating crown dimensions and proximal enamel thickness in a sample of 40 extracted sound, human, mandibular, second bicuspids (20 right and 20 left. Mesiodistal, cervico-occlusal and buccolingual crown dimensions were measured using a digital caliper, accurate to 0.01 mm. Teeth were embedded in acrylic resin and cut along their long axes through the proximal surfaces to obtain 0.7 mm-thick central sections. Enamel thickness on the cut sections was measured using a perfilometer. Comparative analyses were carried out using the Student's-t test (α= 5%. The mean mesiodistal crown widths for right and left teeth were 7.79 mm (± 0.47 and 7.70 mm (± 0.51, respectively. Mean cervico-occlusal heights ranged from 8.31 mm (± 0.75 on the right to 8.38 mm (± 0.85 on the left teeth. The mean values for the buccolingual dimension were 8.67 mm (± 0.70 on the right and 8.65 mm (± 0.54 on the left teeth. The mean enamel thickness on the mesial surfaces ranged from 1.35 mm (± 0.22 to 1.40 mm (± 0.17, on the left and right sides, respectively. On the distal surfaces, the corresponding values were 1.44 mm (± 0.21 and 1.46 mm (± 0.12. No significant differences were found between measurements for right and left teeth. However, enamel thickness was significantly greater on the distal surfaces, compared with the mesial surfaces.

  16. DNA methylation mediated control of gene expression is critical for development of crown gall tumors.

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    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

  17. Wear Behavior of Ceramic CAD/CAM Crowns and Natural Antagonists

    OpenAIRE

    Naumova, Ella A.; Schneider, Stephan; Arnold, Wolfgang H.; Piwowarczyk, Andree

    2017-01-01

    Objective: Evaluation of wear behavior of computer-aided design/computer-aided manufacturing (CAD/CAM) crowns from various restorative materials and natural antagonists. Method: Full CAD/CAM crowns fabricated with nanoceramic resin (Lava Ultimate (LU)), a glass ceramic in a resin interpenetrating matrix (Vita Enamic (VE)) and a lithium silicate reinforced ceramic enriched with zirconia (Vita Suprinity (VS)) were cemented on human molars. The crown and antagonists were subjected to simulated c...

  18. Clinical evaluations of cast gold alloy, machinable zirconia, and semiprecious alloy crowns: A multicenter study.

    Science.gov (United States)

    Park, Ji-Man; Hong, Yong-Shin; Park, Eun-Jin; Heo, Seong-Joo; Oh, Namsik

    2016-06-01

    Few studies have compared the marginal and internal fits of crowns fabricated from machinable palladium-silver-indium (Pd-Ag-In) semiprecious metal alloy. The purpose of this clinical study was to evaluate and compare the marginal and internal fits of machined Pd-Ag-In alloy, zirconia, and cast gold crowns. A prospective clinical trial was performed on 35 participants and 52 abutment teeth at 2 centers. Individuals requiring prosthetic restorations were treated with gold alloy or zirconia crowns (2 control groups) or Pd-Ag-In alloy crowns (experimental group). A replica technique was used to evaluate the marginal and internal fits. The buccolingual and mesiodistal cross-sections were measured, and a noninferiority comparison was conducted. The mean marginal gaps were 68.2 μm for the gold crowns, 75.4 μm for the zirconia crowns, and 76.9 μm for the Pd-Ag-In alloy crowns. In the 5 cross-sections other than the distal cross-section, the 2-sided 95% confidence limits for the differences between the Pd-Ag-In alloy crowns and the 2 control groups were not larger than the 25-μm noninferiority margin. The control groups displayed smaller internal gaps in the line angle and occlusal spaces compared with the Pd-Ag-In crown group. The marginal gaps of machinable Pd-Ag-In alloy crowns did not meet the noninferiority criterion in the distal margin compared with zirconia and gold alloy crowns. Nonetheless, all 3 crowns had clinically applicable precision. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  19. A Comparison of Marginal Fit Between Lithium-Disilicate Press and CAD Fabricated Crowns

    Science.gov (United States)

    2014-05-27

    KBC, Nicholls JI. Evaluation of the marginal fit of a zirconia ceramic computer-aided machined (CAM) crown system. J Prosthet Dent 2010;104:216-27. 7...Workshops _Abstract _Other 6. Title: "A comparison of marginal fit between lithium-disilicate press and CAD fabricated crowns " 7. Intended...thesis manuscript entitled: "A comparison of marginal fit between lithium-disilicate press and CAD fabricated crowns " Is appropriately acknowledged

  20. Fracture Strength of Aged Monolithic and Bilayer Zirconia-Based Crowns

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    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.