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Sample records for cobalt crown carbene

  1. Experimental evidence for cobalt(III)-carbene radicals: key intermediates in cobalt(II)-based metalloradical cyclopropanation

    NARCIS (Netherlands)

    Lu, H.; Dzik, W.I.; Xu, X.; Wojtas, L.; de Bruin, B.; Zhang, X.P.

    2011-01-01

    New and conclusive evidence has been obtained for the existence of cobalt(III)-carbene radicals that have been previously proposed as the key intermediates in the underlying mechanism of metalloradical cyclopropanation by cobalt(II) complexes of porphyrins. In the absence of olefin substrates,

  2. [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.

  3. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  4. Evaluation of marginal/internal fit of chrome‑cobalt crowns: Direct ...

    African Journals Online (AJOL)

    Background and Purpose: The purpose of this study was to evaluate the internal and marginal fit of chrome cobalt (Co‑Cr) crowns were fabricated with laser sintering, computer‑aided design (CAD) and computer‑aided manufacturing, and conventional methods. Materials and Methods: Polyamide master and working ...

  5. 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.

  6. 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.

  7. Retention Load of Telescopic Crowns with Different Taper Angles between Cobalt-Chromium and Polyetheretherketone Made with Three Different Manufacturing Processes Examined by Pull-Off Test.

    Science.gov (United States)

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

    2018-02-01

    To investigate the retention loads of differently fabricated secondary telescopic polyetheretherketone (PEEK) crowns on cobalt-chromium primary crowns with different tapers. Cobalt-chromium primary crowns with 0°, 1°, and 2° tapers were constructed, milled, and sintered. Corresponding secondary crowns were fabricated by milling, pressing from pellets, and pressing from granules. For these nine test groups, the pull-off tests of each crown combination were performed 20 times, and the retention loads were measured (Zwick 1445, 50 mm/min). Data were analyzed using linear regression, covariance analysis, mixed models, Kruskal-Wallis, and Mann-Whitney U-test, together with the Benferroni-Holm correction. The mixed models covariance analysis reinforced stable retention load values (p = 0.162) for each single test sequence. There was no interaction between the groups and the separation cycles (p = 0.179). Milled secondary crowns with 0° showed the lowest mean retention load values compared to all tested groups (p = 0.003) followed by those pressed form pellets with 1°. Regarding the different tapers, no effect of manufacturing method on the results was observed within 1° and 2° groups (p = 0.540; p = 0.052); however, among the 0° groups, the milled ones showed significantly the lowest retention load values (p = 0.002). Among the manufacturing methods, both pressed groups showed no impact of taper on the retention load values (p > 0.324 and p > 0.123, respectively), whereas among the milled secondary crowns, the 0° taper showed significantly lower retention load values than the 1° and 2° taper (p test sequence; however, data with thermo-mechanical aging are still required. In addition, further developments in CAD/CAM manufacturing of PEEK materials for telescopic crowns are warranted, especially for 0°. © 2016 by the American College of Prosthodontists.

  8. Redox noninnocence of carbene ligands: carbene radicals in (catalytic) C-C bond formation

    NARCIS (Netherlands)

    Dzik, W.I.; Zhang, X.P.; de Bruin, B.

    2011-01-01

    In this Forum contribution, we highlight the radical-type reactivities of one-electron-reduced Fischer-type carbenes. Carbene complexes of group 6 transition metals (Cr, Mo, and W) can be relatively easily reduced by an external reducing agent, leading to one-electron reduction of the carbene ligand

  9. Chemistry of Stable Carbenes and «Green» Technologies

    Directory of Open Access Journals (Sweden)

    Korotkikh, N.I.

    2015-11-01

    Full Text Available Brief analysis of fundamental research in the chemistry of stable carbenes and applications in the field of «green» chemistry on their basis carried out at the L.M. Litvinenko Institute of Physical Organic & Coal Chemistry of NAS of Ukraine over the last decade is given. Carbene versions of ester Claisen condensation to form zwitterionic compounds, the Leuckart-Wallach reaction with the autoreduction of carbenoid azolium salts, Hofmann cleavage of aminocarbene insertion products, an induced tandem autotransformation of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles were found. New carbene reactions of ad dition, deesterification, oxidation and complexation were revealed. Effective methods of obtaining stable carbenes and carbenoids were suggested. New types of carbenes, namely benzimidazolylidenes, superstable conjugated biscarbenes and new types of carbenoids were synthesized. The existence of hypernucleophilic carbenes was theoretically predicted and experimentally confirmed. The prospects of the use of carbenes and their derivatives, in particular, carbene complexes of transition metals in catalysis of organic reactions and the search of biologically active compounds were shown.

  10. Insights Into the Carbene-Initiated Aggregation of [Fe(cot)2

    KAUST Repository

    Lavallo, Vincent; El-Batta, Amer; Bertrand, Guy; Grubbs, Robert H.

    2010-01-01

    Carbenes attack! Stable carbenes react with [Fe(cot)2] in very different ways. Whereas the classical N-heterocyclic carbenes induce the formation of tetra- and trimetallic iron clusters, abnormal NHCs and carbocyclic carbenes (BACs) form mono- and bimetallic iron complexes. Cyclic (alkyl)(amino)carbenes (CAACs) react with [Fe(cot)2] in a completely different manner, namely through outersphere [4+1] cycloaddition.

  11. Insights Into the Carbene-Initiated Aggregation of [Fe(cot)2

    KAUST Repository

    Lavallo, Vincent

    2010-11-25

    Carbenes attack! Stable carbenes react with [Fe(cot)2] in very different ways. Whereas the classical N-heterocyclic carbenes induce the formation of tetra- and trimetallic iron clusters, abnormal NHCs and carbocyclic carbenes (BACs) form mono- and bimetallic iron complexes. Cyclic (alkyl)(amino)carbenes (CAACs) react with [Fe(cot)2] in a completely different manner, namely through outersphere [4+1] cycloaddition.

  12. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  13. [The study of the colorimetric characteristics of the cobalt-chrome alloys abutments covered by four different all-ceramic crowns by using dental spectrophotometer].

    Science.gov (United States)

    Chen, Yifan; Liu, Hongchun; Meng, Yukun; Chao, Yonglie; Liu, Changhong

    2015-06-01

    This study aims to evaluate the optical data of the different sites of the cobalt-chrome (Co-Cr) alloy abutments covered by four different all-ceramic crowns and the color difference between the crowns and target tab using a digital dental spectrophotometer. Ten Co-Cr alloy abutments were made and tried in four different groups of all-ceramic crowns, namely, Procera aluminia, Procera zirconia, Lava zirconia (Lava-Zir), and IPS E.max glass-ceramic lithium disilicate-reinforced monolithic. The color data of the cervical, body, and incisal sites of the samples were recorded and analyzed by dental spectrophotometer. The CIE L*, a*, b* values were again measured after veneering. The color difference between the abutments covered by all-ceramic crowns and A2 dentine shade tab was evaluated. The L* and b* values of the abutments can be increased by all of the four groups of all-ceramic copings, but a* values were decreased in most groups. A statistical difference was observed among four groups. After being veneered, the L* values of all the copings declined slightly, and the values of a*, b* increased significantly. When compared with A2 dentine shade tab, the ΔE of the crowns was below 4. Four ceramic copings were demonstrated to promote the lightness and hue of the alloy abutments effecttively. Though the colorimetric baseline of these copings was uneven, veneer porcelain can efficiently decrease the color difference between the samples and thee target.

  14. Uranium nucleophilic carbene complexes

    International Nuclear Information System (INIS)

    Tourneux, Jean-Christophe

    2012-01-01

    The only stable f-metal carbene complexes (excluding NHC) metals f present R 2 C 2- groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the di-anion C{Ph 2 P(=S)} 2 2- (SCS 2- ) to extend the organometallic chemistry of this element in its various oxidation states (+3-+6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U. We first isolated the reactants M(SCHS) (M = Li and K) and demonstrated the role of the cation M + on the evolution of the di-anion M 2 SCS (M = Li, K, Tl) which is transformed into LiSCHS in THF or into product of intramolecular cyclization K 2 [C(PhPS) 2 (C 6 H 4 )]. We have developed the necessary conditions mono-, bis- and tris-carbene directly from the di-anion SCS 2- and UCl 4 , as the precursor used in uranium chemistry. The protonolysis reactions of amides compounds (U-NEt 2 ) by the neutral ligand SCH 2 S were also studied. The compounds [Li(THF)] 2 [U(SCS)Cl 3 ] and [U(SCS)Cl 2 (THF) 2 ] were then used to prepare a variety of cyclopentadienyl and mono-cyclo-octa-tetra-enyliques uranium(IV) carbene compounds of the DFT analysis of compounds [M(SCS)Cl 2 (py) 2 ] and [M(Cp) 2 (SCS)] (M = U, Zr) reveals the strong polarization of the M=C double bond, provides information on the nature of the σ and π interactions in this binding, and shows the important role of f orbitals. The influence of ancillary ligands on the M=C bond is revealed by examining the effects of replacing Cl - ligands and pyridine by C 5 H 5 - groups. Mulliken and NBO analyzes show that U=C bond, unlike the Zr=C bond, is not affected by the change in environment of the metal center. While the oxidation tests of carbene complexes of U(IV) were disappointing, the first carbene complex of uranium (VI), [UO 2 (SCS)(THF) 2 ], was isolated with the uranyl ion UO 2 2+ . The reactions of compounds UO 2 X 2

  15. Studies of coal structure using carbene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The object of this grant was to react coal, derivatized forms of coal, and solvent swelled coal with carbenes (divalent carbon species) under mild conditions. These carbenes were to be prepared by treating the coal with several diazo compounds and then thermally decomposing them at relatively low temperatures (80--130{degree}C). The carbenes were to be chosen to show varying selectively toward aromatic rings containing heteroatom functionalities and toward polynuclear aromatic systems. In some instances, where selectivities toward aromatic and heteroaromatic ring systems were not known, model studies were to be carried out. Because of the generally mild conditions employed and the good selectivity anticipated, and actually observed with one particular system, it was expected that this methodology would provide structural information about the coal, along with data on the extent of occurrence and type of aromatic systems. After carbene reactions, treatment of the coal samples was to include extractions and thermolysis. Physical studies included thermogravimetric analysis, diffuse reflectance FT-IR spectroscopy, NMR ({sup 1}H and {sup 13}C) spectroscopy, gas chromatography, GC/MS and GC/FT-IR. 7 figs., 10 tabs.

  16. Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

    Directory of Open Access Journals (Sweden)

    Mário M. Q. Simões

    2018-03-01

    Full Text Available Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

  17. A one-dimensional polymeric cobalt(III–potassium complex with 18-crown-6, cyanide and porphyrinate ligands

    Directory of Open Access Journals (Sweden)

    Yassine Belghith

    2014-03-01

    Full Text Available The reaction of CoII(TpivPP {TpivPP is the dianion of 5,10,15,20-tetrakis[2-(2,2-dimethylpropanamidophenyl]porphyrin} with an excess of KCN salts and an excess of the 18-crown-6 in chlorobenzene leads to the polymeric title compound catena-poly[[dicyanido-2κ2C-(1,4,7,10,13,16-hexaoxacyclooctadecane-1κ6O{μ3-(2α,2β-5,10,15,20-tetrakis[2-(2,2-dimethylpropanamidophenyl]porphyrinato-1κO5:2κ4N,N′,N′′,N′′′:1′κO15}cobalt(IIIpotassium] dihydrate], {[CoK(CN2(C12H24O6(C64H64N8O4]·2H2O}n. The CoIII ion lies on an inversion center, and the asymmetric unit contains one half of a [CoIII(2α,2β-TpivPP(CN2]− ion complex and one half of a [K(18-C-6]+ counter-ion (18-C-6 is 1,4,7,10,13,16-hexaoxacyclooctadecane, where the KI ion lies on an inversion center. The CoIII ion is hexacoordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The KI ion is chelated by the six O atoms of the 18-crown-6 molecule and is further coordinated by two O atoms of pivalamido groups of the porphyrin ligands, leading to the formation of polymeric chains running along [011]. In the crystal, the polymeric chains and the lattice water molecules are linked by N—H...O and O—H...N hydrogen bonds, as well as weak C—H...O, O—H...π and C—H...π interactions into a three-dimensional supramolecular architecture.

  18. Functional (co)polymers from carbenes: scope, mechanism & polymer properties

    NARCIS (Netherlands)

    Franssen, N.M.G.

    2012-01-01

    Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

  19. The reactions of anthronylidene carbene with some heterocyclic compounds

    International Nuclear Information System (INIS)

    Divisia, Bernadette

    1970-01-01

    The action of the anthronylidene carbene, generated by photochemical decomposition of 9-diazo 10-anthron, on four heterocyclic compounds (furan, thiophene, 1-methyl-pyrrole and 2,5-dihydrofuran) has been examined. Two classical carbene reactions have been observed: the addition on double bond (furan, thiophene, 1-methylpyrrole) and hydrogen atom abstraction of the heterocyclic compound (2,5-dihydrofuran). In the case of furan and thiophene, the cyclo-propanic compound resulting from the addition is spontaneously transformed into an ethylenic derivative by valence isomerization. The furan derivative undergoes a cis-trans isomerization, while the thiophene one undergoes an extra carbene attack. In the case of 1-methylpyrrole, the corresponding cyclo-propanic compound undergoes a ring cleavage, followed by a hydrogen atom migration leading to the formation of a substituted anthron. Only an allylic hydrogen atom selective abstraction of heterocyclic compound takes place in the reaction of anthronylidene carbene with 2,5-dihydrofuran. The asymmetrical coupling of radicals so obtained yields the corresponding substituted anthron. (author) [fr

  20. N,N'-diamidoketenimines via coupling of isocyanides to an N-heterocyclic carbene.

    Science.gov (United States)

    Hudnall, Todd W; Moorhead, Eric J; Gusev, Dmitry G; Bielawski, Christopher W

    2010-04-16

    Treatment of an N-heterocyclic carbene that features two amide groups N-bound to the carbene nucleus with various organic isocyanides afforded a new class of ketenimines in yields of up to 96% (isolated). DFT analyses revealed that the carbene exhibits a unique, low-lying LUMO, which may explain the atypical reactivity observed.

  1. Evaluation of marginal/internal fit of chrome-cobalt crowns: Direct laser metal sintering versus computer-aided design and computer-aided manufacturing.

    Science.gov (United States)

    Gunsoy, S; Ulusoy, M

    2016-01-01

    The purpose of this study was to evaluate the internal and marginal fit of chrome cobalt (Co-Cr) crowns were fabricated with laser sintering, computer-aided design (CAD) and computer-aided manufacturing, and conventional methods. Polyamide master and working models were designed and fabricated. The models were initially designed with a software application for three-dimensional (3D) CAD (Maya, Autodesk Inc.). All models were fabricated models were produced by a 3D printer (EOSINT P380 SLS, EOS). 128 1-unit Co-Cr fixed dental prostheses were fabricated with four different techniques: Conventional lost wax method, milled wax with lost-wax method (MWLW), direct laser metal sintering (DLMS), and milled Co-Cr (MCo-Cr). The cement film thickness of the marginal and internal gaps was measured by an observer using a stereomicroscope after taking digital photos in ×24. Best fit rates according to mean and standard deviations of all measurements was in DLMS both in premolar (65.84) and molar (58.38) models in μm. A significant difference was found DLMS and the rest of fabrication techniques (P 0.05). DMLS was best fitting fabrication techniques for single crown based on the results.The best fit was found in marginal; the larger gap was found in occlusal.All groups were within the clinically acceptable misfit range.

  2. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry and Photon Science Inst.

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6).

  3. Rhenium carbene complexes and their applications; Rhenium-Carben-Komplexe und ihre Anwendungen

    Energy Technology Data Exchange (ETDEWEB)

    Hille, Claudia Heidi

    2016-01-25

    New pharmaceutically suitable metal complexes play an important role in the development of diagnostic and therapeutic agents for cancer treatment. One option concerning new radiopharmaceuticals, is the application of the rhenium isotopes {sup 186}Re and {sup 188}Re. Therefore, water soluble but at the same time stable complexes, which can be synthesized straightforward, are required. In this thesis, several synthetic pathways to such rhenium complexes bearing Nheterocyclic carbenes are presented and applicability tests of literature known complexes conducted. The selected target structures based on monocarbenes turned out to be inappropriate for use in radiopharmaceutical applications, due to their long reaction times and purification issues. Additionally, sterical and electronical effects of the carbene ligands concerning complex formation have been investigated. Possibilities of functionalization at different positions on the heterocycle as well as hydrophilic wingtips - to achieve a better stability in an aqueous media - have been examined to gain information about chemical and physical properties of the resulting complexes. Furthermore, experiments regarding the coordination of various biscarbene ligands, which provides besides the stable chelatisation additionally the possibility of varying the linking bridge, to rhenium(I/V) precursors, have been performed. Dioxo-bis-(1,1{sup '}-methylene-bis(3,3{sup '}-diisopropylimidazolium-2-ylidene)) rhenium(V )-hexafluorophosphate was synthesized via a transmetalation reaction of the corresponding silver carbene with ReOCl{sub 3}(PPh{sub 3}){sub 2} and silver hexafluorophosphate. This complex provided the basis for the first radiolabeled {sup 188}Rhenium NHC complex later on. An enhancement of the kinetic and thermodynamic stability of potential rhenium biscarbene complexes based on modifications concerning the length and character of the bridging moiety between the chelating NHC rings as well as the nature of

  4. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6). (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

    2013-01-01

    A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

  6. Catalytic Asymmetric C–H Insertions of Rhodium(II) Azavinyl Carbenes

    OpenAIRE

    Chuprakov, Stepan; Malik, Jamal A.; Zibinsky, Mikhail; Fokin, Valery V.

    2011-01-01

    A highly efficient enantioselective C–H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C–H functionalization of alkanes to access a variety of β-chiral sulfonamides.

  7. Experimental and theoretical investigations on the high-electron donor character of pyrido-annelated N-heterocyclic carbenes

    Directory of Open Access Journals (Sweden)

    Michael Nonnenmacher

    2016-08-01

    Full Text Available Rh(CO2Cl(NHC complexes of dipyrido-annelated N-heterocyclic carbenes were prepared. From the C–H coupling constant of the respective imidazolium salts and the N–C–N angle of the N-heterocyclic carbene (NHC, a weaker σ-donor character than that of typical unsaturated NHCs is expected. However, the IR stretching frequencies of their Rh(CO2Cl complexes suggest an electron-donor character even stronger than that of saturated NHCs. We ascribe this to the extremely weak π-acceptor character of the dipyrido-annelated NHCs caused by the conjugated 14 πe− system that thus allows for an enhanced Rh–CO backbonding. This extremely low π-acceptor ability is also corroborated by the 77Se NMR chemical shift of −55.8 ppm for the respective selenourea, the lowest value ever measured for imidazole derived selenoureas. DFT-calculations of the free carbene confirm the low σ-donor character by the fact that the σ-orbital of the carbene is the HOMO−1 that lies 0.58 eV below the HOMO which is located at the π-system. Natural population analysis reveals the lowest occupation of the pπ-orbital for the saturated carbene carbon atom and the highest for the pyrido-annelated carbene. Going from the free carbene to the Rh(CO2Cl(NHC complexes, the increase in occupancy of the complete π-system of the carbene ligand upon coordination is lowest for the pyrido-annelated carbene and highest for the saturated carbene.

  8. Formation of quinones, indanones and furans by the reaction of molybdenum carbene complexes with alkynes

    International Nuclear Information System (INIS)

    Doetz, K.H.; Larbig, H.

    1992-01-01

    (Alkoxy)carbene complexes of molybdenum react with terminal alkynes to give carbene annulation of cycloaddition products, the skeleton of which depends on the carbene substitution pattern and the alkyne used. (CO) 5 Mo=C(OMe)-p-tol undergoes carbene annulation upon reaction with trimethylsilylacetylene leading to naphthoquinone after oxidative work-up. Similar products are obtained from (CO) 5 Mo=C(OMe)2-furyl and hex-1-yne or oct-1-yne. The reaction of these alkynes results in the formation of indanones as five-membered annulation products. In the presence of 3.3-dimethylbut-1-yne the (phenyl) carbene ligands act as a C 1 -synthon, which is incorporated into the furan cycloaddition products

  9. From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer

    Directory of Open Access Journals (Sweden)

    Ming Liu

    2016-12-01

    Full Text Available The mesomeric betaine imidazolium-1-ylphenolate forms a borane adduct with tris(pentafluorophenylborane by coordination with the phenolate oxygen, whereas its NHC tautomer 1-(2-phenolimidazol-2-ylidene reacts with (triphenylphosphinegold(I chloride to give the cationic NHC complex [Au(NHC2][Cl] by coordination with the carbene carbon atom. The anionic N-heterocyclic carbene 1-(2-phenolateimidazol-2-ylidene gives the complexes [K][Au(NHC−2], [Rh(NHC−3] and [Ni(NHC−2], respectively. Results of four single crystal analyses are presented.

  10. Nitrene-carbene-carbene rearrangement. Photolysis and thermolysis of tetrazolo[5,1- a ]phthalazine with formation of 1-phthalazinylnitrene, o-cyanophenylcarbene, and phenylcyanocarbene

    DEFF Research Database (Denmark)

    Høj, Martin; Kvaskoff, David; Wentrup, Curt

    2014-01-01

    ). The rearrangement of 12 â., 13 â., 14 constitutes a carbene-carbene rearrangement. 1-Phthalazinylnitrene 310 is observed by means of its UV-vis spectrum in Ar matrix following FVT of 9 above 550 C. Rearrangement to cyanophenylcarbenes also takes place on FVT of 9 as evidenced by observation of the products of ring...... contraction, viz., fulvenallenes and ethynylcyclopentadienes 16-18. Thus the overall rearrangement 10 → 11 → 12 â., 13 â., 14 can be formulated. © 2013 American Chemical Society....

  11. Unexpected rearrangements in the synthesis of an unsymmetrical tridentate dianionic N-heterocyclic carbene

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle; Miqueu, Karinne; Sotiropoulos, Jean-Marc; Henling, Lawrence M.; Day, Michael W.; Labinger, Jay A.; Bercaw, John E.

    2013-01-01

    Starting from the same ethylenediamine species, three valuable carbene precursors were synthesized under differing conditions: a tridentate dianionic N-heterocyclic carbene bearing an aniline, a phenol and a central dihydroimidazolium salt, its benzimidazolium isomer by intramolecular rearrangement and a dicationic benzimidazolium-benzoxazolium salt by changing the Brønsted acid from HCl to HBF4. A DFT study was performed to understand the rearrangement pathway. The structure of a bis[(NCO)carbene] zirconium complex was determined. © 2013 The Royal Society of Chemistry.

  12. Chemical functionalization of graphene by carbene cycloaddition: A density functional theory study

    International Nuclear Information System (INIS)

    Zan, Wenyan

    2014-01-01

    Graphical abstract: - Highlights: • The reaction process of graphene functionalization with CCl 2 group in atomic scales was studied. • The potential candidate carbenes CR 2 (R = H, F, CN, NO 2 0 , NO 2 90 , CH 3 , OCH 3 , CCH, C 6 H 5 ) were separately combined with graphene. • The functionalization of graphene nanoribbon with dichlorocarbene group was investigated. • The electronic properties of graphene functionalized by carbene groups were discussed. - Abstract: In this work, we have systematically studied the structural, energetic and electronic properties of graphene functionalized with carbene groups by using density functional theory. Introducing a low concentration of CCl 2 group in graphene was studied in detail by DFT, and closed cyclopropane-like three-membered ring structure was formed, meanwhile, the potential candidate carbene groups CR 2 (R = H, F, CH 3 , CN, NO 2 , OCH 3 , CCH, C 6 H 5 ) were added to graphene sheet, and CR 2 (R = H, NO 2 , CH 3 ) groups were expected to be good reactive species to covalently modify graphene. The graphene functionalization with carbene groups above can open graphene's band gap. More CCl 2 molecules were added to graphene, and different concentrations of CCl 2 group can tune graphene's band gap. In addition, the addition of CCl 2 group to graphene edges was investigated, and the stronger binding energy was found. Multiple CCl 2 molecules preferred to be bound with the same edge of graphene nanoribbon. This work provides an insight into the detailed molecular mechanism of graphene functionalization with carbene groups

  13. Synthesis and structure of the unligated carbene of chromium

    Energy Technology Data Exchange (ETDEWEB)

    Billups, W.E.; Souchan Chang; Hauge, R.H.; Margrave, J.L. (Rice Univ., Houston, TX (United States))

    1993-04-14

    Complexes with metal-carbon double bonds have found applications as intermediates in many important catalytic reactions including cyclopropanation of alkenes by diazoalkanes, Fischer-Tropsch synthesis, olefin metathesis, Ziegler-Natta polymerization, alkane activation, and in the decomposition of transition metal alkyl complexes. However, complexes with the simplest carbene, CH[sub 2], coordinated to the metal center are relatively rare. In this paper the authors report the synthesis and characterization of the simple unligated carbene of chromium by FTIR matrix isolation spectroscopy. 7 refs., 3 figs., 4 tabs.

  14. Comparative reactivity of different types of stable cyclic and acyclic mono- and diamino carbenes with simple organic substrates.

    Science.gov (United States)

    Martin, David; Canac, Yves; Lavallo, Vincent; Bertrand, Guy

    2014-04-02

    A series of stable carbenes, featuring a broad range of electronic properties, were reacted with simple organic substrates. The N,N-dimesityl imidazolylidene (NHC) does not react with isocyanides, whereas anti-Bredt di(amino)carbene (pyr-NHC), cyclic (alkyl)(amino)carbene (CAAC), acyclic di(amino)carbene (ADAC), and acyclic (alkyl)(amino)carbene (AAAC) give rise to the corresponding ketenimines. NHCs are known to promote the benzoin condensation, and we found that the CAAC, pyr-NHC, and ADAC react with benzaldehyde to give the ketone tautomer of the Breslow intermediate, whereas the AAAC first gives the corresponding epoxide and ultimately the Breslow intermediate, which can be isolated. Addition of excess benzaldehyde to the latter does not lead to benzoin but to a stable 1,3-dioxolane. Depending on the electronic properties of carbenes, different products are also obtained with methyl acrylate as a substrate. The critical role of the carbene electrophilicity on the outcome of reactions is discussed.

  15. Fullerene–Carbene Lewis Acid–Base Adducts

    KAUST Repository

    Li, Huaping; Risko, Chad; Seo, Jung Hwa; Campbell, Casey; Wu, Guang; Brédas, Jean-Luc; Bazan, Guillermo C.

    2011-01-01

    The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths

  16. A dual Lewis base activation strategy for enantioselective carbene-catalyzed annulations.

    Science.gov (United States)

    Izquierdo, Javier; Orue, Ane; Scheidt, Karl A

    2013-07-24

    A dual activation strategy integrating N-heterocyclic carbene (NHC) catalysis and a second Lewis base has been developed. NHC-bound homoenolate equivalents derived from α,β-unsaturated aldehydes combine with transient reactive o-quinone methides in an enantioselective formal [4 + 3] fashion to access 2-benzoxopinones. The overall approach provides a general blueprint for the integration of carbene catalysis with additional Lewis base activation modes.

  17. A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.

    Science.gov (United States)

    Zhang, Liming

    2014-03-18

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  18. A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

    Science.gov (United States)

    2015-01-01

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  19. Nature of strontium extraction by synergistic mixtures of chlorinated cobalt dicarbollide and polyethers

    International Nuclear Information System (INIS)

    Smirnov, I.V.; Stoyanov, E.S.; Vorob'eva, T.P.

    2003-01-01

    Extraction of strontium by synergistic mixtures of chlorinated cobalt dicarbollide (DCC) with different polyethers was studied. In the acidic media the distribution coefficients (D(Sr)) decreases in the order 15-crown-5 > PEG-400 > 18-crown-6 and does not correspond to the row of constants stability of the strontium complexes with these polyethers. When passing to the salt media (Li and Na nitrates) the row of D(Sr) is changed: PEG-400 > 18 crown 6 > 15 crown 5. IR-spectroscopy study has shown that in synergistic mixtures the proton forms [H 5O2 + .PEG], [H 5O2 + .(15-crown-5)2] and [H 3 O + .(18 crown 6)] cations, which are exchange on Sr 2+ resulting to formation [Sr 2+ .PEG], [Sr 2+ .(15-crown-5)2] and [Sr 2+ .(18-crown-6)(H 2 O)n] cations correspondingly. The PEG-400 is the best among polyethylene glycols, since its all six COC groups and two even more active OH groups complete the first co-ordination sphere of Sr 2+ . Extremely low extractability of Sr 2+ from acidic media in the presence of 18-crown-6 as compared with 15-crown-5 is mainly caused by the high stability of the [H 3 O + .(18-crown-6)] cation that is responsible for less extractable hydrated Sr complex formation. (author)

  20. Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

    Science.gov (United States)

    Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

    2014-01-01

    Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

  1. Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry.

    Science.gov (United States)

    Wentrup, Curt

    2018-05-29

    There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years due to the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered. Numerous rearrangements and fragmentations have been documented. This minireview aims to give an overview of some of these developments but will not generally cover laser flash photolysis and chemical reactions in liquid solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. FEM and Von Mises Analysis on Prosthetic Crowns Structural Elements: Evaluation of Different Applied Materials.

    Science.gov (United States)

    Bramanti, Ennio; Cervino, Gabriele; Lauritano, Floriana; Fiorillo, Luca; D'Amico, Cesare; Sambataro, Sergio; Denaro, Deborah; Famà, Fausto; Ierardo, Gaetano; Polimeni, Antonella; Cicciù, Marco

    2017-01-01

    The aim of this paper is to underline the mechanical properties of dental single crown prosthodontics materials in order to differentiate the possibility of using each material for typical clinical condition and masticatory load. Objective of the investigation is to highlight the stress distribution over different common dental crowns by using computer-aided design software and a three-dimensional virtual model. By using engineering systems of analyses like FEM and Von Mises investigations it has been highlighted the strength over simulated lower first premolar crowns made by chrome cobalt alloy, golden alloy, dental resin, and zirconia. The prosthodontics crown models have been created and put on simulated chewing stresses. The three-dimensional models were subjected to axial and oblique forces and both guaranteed expected results over simulated masticatory cycle. Dental resin presented the low value of fracture while high values have been recorded for the metal alloy and zirconia. Clinicians should choose the better prosthetic solution for the teeth they want to restore and replace. Both prosthetic dental crowns offer long-term success if applied following the manufacture guide limitations and suggestions.

  3. The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids

    Science.gov (United States)

    Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.

    2010-01-01

    The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

  4. Zinc-Catalyzed Synthesis of Conjugated Dienoates through Unusual Cross-Couplings of Zinc Carbenes with Diazo Compounds.

    Science.gov (United States)

    Mata, Sergio; González, María J; González, Jesús; López, Luis A; Vicente, Rubén

    2017-01-23

    Zinc-catalyzed selective cross-coupling of two carbene sources, such as vinyl diazo compounds and enynones, enabled the synthesis of conjugated dienoate derivatives. This reaction involved the unprecedented coupling of a zinc furyl carbene with vinyl diazo compounds through the γ-carbon. Alternatively, dienoates were also prepared by a commutative cross-coupling of zinc vinyl carbenes generated from cyclopropenes and simple diazo compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Diphenylcarbene Protected by Four ortho-Iodine Groups: An Unusually Persistent Triplet Carbene

    Directory of Open Access Journals (Sweden)

    Katsuyuki Hirai

    2016-11-01

    Full Text Available Diphenyldiazomethane with four iodine groups at the ortho positions and two tert-butyl groups at the para positions, i.e., bis(4-tert-butyl-2,6-diiodophenyldiazomethane (1a-N2, was synthesized as a sterically hindered triplet carbene precursor. Irradiation of 1a-N2 in solution effectively generated the corresponding triplet diphenylcarbene 31a, which was characterized by UV-vis spectroscopy at low temperature, along with laser flash photolysis techniques at room temperature. The UV-vis spectrum of 31a was obtained by irradiating 1a-N2 in a 2-methyltetrahydrofuran matrix at 77 K. The ESR spectrum showed no triplet carbene signals, while a radical species was observed at the anticipated temperature of the decomposition of triplet carbene 31a. Transient absorption bands ascribable to 31a were observed by laser flash photolysis of 1a-N2 in a degassed benzene solution and decayed very slowly with a second-order rate constant (2k/εl of 5.5 × 10−3·s−1. Steady-state irradiation of 1a-N2 in degassed benzene afforded 9,10-diarylphenanthrene derivative 2a in a 31% yield. Triplet carbene 31a was also trapped by either oxygen (kO2 = 6.5 × 105 M−1·s−1 or 1,4-cyclohexadiene (kCHD = 1.5 M−1·s−1 to afford the corresponding ketone 1a-O or the diarylmethane 1a-H2. The carbene was shown to be much less reactive than the triplet diphenylcarbene that is protected by two ortho-iodo and two ortho-bromo groups, 31b.

  6. Influence of cement film thickness on the retention of implant-retained crowns.

    Science.gov (United States)

    Mehl, Christian; Harder, Sönke; Steiner, Martin; Vollrath, Oliver; Kern, Matthias

    2013-12-01

    The main goal of this study was to establish a new, high precision procedure to evaluate the influence of cement film thickness on the retention of cemented implant-retained crowns. Ninety-six tapered titanium abutments (6° taper, 4.3 mm diameter, Camlog) were shortened to 4 mm. Computer-aided design was used to design the crowns, and selective laser sintering, using a cobalt-chromium alloy, was used to produce the crowns. This method used a focused high-energy laser beam to fuse a localized region of metal powder to build up the crowns gradually. Before cementing, preset cement film thicknesses of 15, 50, 80, or 110 μm were established. Glass ionomer, polycarboxylate, or resin cements were used for cementation. After 3 days storage in demineralized water, the retention of the crowns was measured in tension using a universal testing machine. The cement film thicknesses could be achieved with a high level of precision. Interactions between the factors cement and cement film thickness could be found (p ≤ 0.001). For all cements, crown retention decreased significantly between a cement film thickness of 15 and 50 μm (p ≤ 0.001). At 15 μm cement film thickness, the resin cement was the most retentive cement, followed by the polycarboxylate and then the glass ionomer cement (p ≤ 0.05). The results suggest that cement film thickness has an influence on the retentive strength of cemented implant-retained crowns. © 2013 by the American College of Prosthodontists.

  7. Abstraction of methyl from neutral Fischer-type carbene complexes: A new site for nucleophilic attack

    Energy Technology Data Exchange (ETDEWEB)

    Toomey, L.M.; Atwood, J.D. [State Univ. of New York, Buffalo, NY (United States)

    1997-02-04

    Reactions of Fischer-type carbene complexes, M(CO){sub 5}(C(OMe)pH) (M = Cr, W), with metal carbonyl anions (M`{sup -} = CpFe(CO){sub 2}{sup -@}, Re(CO){sub 5}{sup -}, Mn(CO){sub 4}PPh{sub 3}{sup -}, Co(CO){sub 3}PPh{sub 3}{sup -}, Cp{sup *}Cr(CO){sub 3}{sup -}, CpMo(CO){sub 3}{sup -}) result in demethylation of the carbene complexes. The products are M(CO){sub 5}C(O)Ph{sup -} and M`-Me, characterized by infrared and NMR spectroscopy. A slower rate for reaction with W(CO){sub 5}(C(OEt)Ph) in comparison to the methyl analogue is consistent with nucleophilic attack of the metal carbonyl anion on the methyl of the methoxy group of the carbene. This is a new type of nucleophilic attack of a Fischer-type carbene. 22 refs., 1 fig., 1 tab.

  8. Rhodium (II) carbene C-H insertion in water and catalyst reuse

    International Nuclear Information System (INIS)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M.

    2007-01-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh 2 (OAc) 4 . The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  9. -Heterocyclic Carbene Complexes of Mineral Acids

    KAUST Repository

    Brill, Marcel; Nahra, Fady; Gó mez-Herrera, Alberto; Zinser, Caroline; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.

    2016-01-01

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  10. -Heterocyclic Carbene Complexes of Mineral Acids

    KAUST Repository

    Brill, Marcel

    2016-11-08

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  11. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  12. FEM and Von Mises Analysis on Prosthetic Crowns Structural Elements: Evaluation of Different Applied Materials

    Directory of Open Access Journals (Sweden)

    Ennio Bramanti

    2017-01-01

    Full Text Available The aim of this paper is to underline the mechanical properties of dental single crown prosthodontics materials in order to differentiate the possibility of using each material for typical clinical condition and masticatory load. Objective of the investigation is to highlight the stress distribution over different common dental crowns by using computer-aided design software and a three-dimensional virtual model. By using engineering systems of analyses like FEM and Von Mises investigations it has been highlighted the strength over simulated lower first premolar crowns made by chrome cobalt alloy, golden alloy, dental resin, and zirconia. The prosthodontics crown models have been created and put on simulated chewing stresses. The three-dimensional models were subjected to axial and oblique forces and both guaranteed expected results over simulated masticatory cycle. Dental resin presented the low value of fracture while high values have been recorded for the metal alloy and zirconia. Clinicians should choose the better prosthetic solution for the teeth they want to restore and replace. Both prosthetic dental crowns offer long-term success if applied following the manufacture guide limitations and suggestions.

  13. An unprecedented chemospecific and stereoselective tandem nucleophilic addition/cycloaddition reaction of nucleophilic carbenes with ketenimines.

    Science.gov (United States)

    Cheng, Ying; Ma, Yang-Guang; Wang, Xiao-Rong; Mo, Jun-Ming

    2009-01-16

    The first study of the reaction between nucleophilic carbenes and ketenimines is reported. The interaction of thiazole and benzothiazole carbenes with ketenimines proceeded in a chemospecific and stereoselective manner to produce thiazole- and benzothiazole-spiro-pyrrole derivatives generally in good yields. The reaction was proposed to proceed via a tandem nucleophilic addition of carbene to the C=N bond of ketenimine followed by a stepwise [3+2] cycloaddition of the 1,3-dipolar intermediate with the C=C bond of ketenimine. This reaction provides a powerful protocol for the construction of novel polyfunctional thiazole-spiro-pyrrole or benzothiazole-spiro-pyrrole compounds that are not readily accessible by other methods.

  14. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    Science.gov (United States)

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-08

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors.

    Science.gov (United States)

    Wang, Bo; Yi, Heng; Zhang, Hang; Sun, Tong; Zhang, Yan; Wang, Jianbo

    2018-01-19

    Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

  16. N-heterocyclic carbene complexes of silver and gold as novel tools against breast cancer progression.

    Science.gov (United States)

    Saturnino, Carmela; Barone, Ines; Iacopetta, Domenico; Mariconda, Annaluisa; Sinicropi, Maria Stefania; Rosano, Camillo; Campana, Antonella; Catalano, Stefania; Longo, Pasquale; Andò, Sebastiano

    2016-12-01

    Metal carbenic complexes have received considerable attention in both the catalysis and biological fields for their potential applications in cancer and antimicrobial therapies. A small series of new silver and gold N-heterocyclic carbene complexes has been designed and synthesized. Among the tested complexes, one compound was particularly active in inhibiting anchorage-dependent and -independent breast cancer proliferation, and inducing cell apoptosis via a mitochondria-related process. The antitumor activity was associated to the transcriptional activation of the tumor suppressor gene p53 in an Sp1-dependent manner, as evidenced by biological and docking studies. Our results highlight the importance and the versatility of N-heterocyclic carbene complexes of gold and silver as useful tools against breast cancer progression.

  17. Synthesis and Characterization of Ag(I) and Pd(II) Complexes with a Pyridine Substituted N-Heterocyclic Carbene Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ga Young; Jung, Hyun Jin; Lee, Dong Heon [Chonbuk National Univ., Jeonju (Korea, Republic of); Park, Gyung Se [Kunsan National Univ., Kunsan (Korea, Republic of)

    2010-06-15

    We have used our new tridentate pyridine substituted N-heterocyclic carbene to generate an interesting trinuclear [((MepyCH{sub 2}){sub 2}-Im){sub 3}Ag{sub 3}]{sup 3+} complex, displaying very short Ag-Ag separations. A Pd(II)-NHC complex was prepared from [((MepyCH{sub 2}){sub 2}-Im){sub 3}Ag{sub 3}]{sup 3+} via a facile transmetallation, leading to a dimeric [(MepyCH{sub 2}){sub 2}-ImPdCl]{sub 2}{sup 2+} complex. Future plans are underway for the survey of the potential applications of these new NHC complexes as luminesent materials or homogeneous catalysts. Since Arduengo's discovery of the first isolable free carbene in 1991, N-heterocyclic carbenes (NHC) have been extensively utilized as ligands for transition metals. NHC are generally more stable than two extreme types of carbenes, the Fischer and the Schrock carbenes. They are good σ donors like most tertiary phosphins, PR{sub 3}, but the π-bonding with the metal is rather weak. The thriving studies of NHC-coordinated metal complexes produced a wide range of applications from homogeneous catalysts to materials science.

  18. N-Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu.

    Science.gov (United States)

    Jiang, Li; Zhang, Bodong; Médard, Guillaume; Seitsonen, Ari Paavo; Haag, Felix; Allegretti, Francesco; Reichert, Joachim; Kuster, Bernhard; Barth, Johannes V; Papageorgiou, Anthoula C

    2017-12-01

    By means of scanning tunnelling microscopy (STM), complementary density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS) we investigate the binding and self-assembly of a saturated molecular layer of model N -heterocyclic carbene (NHC) on Cu(111), Ag(111) and Au(111) surfaces under ultra-high vacuum (UHV) conditions. XPS reveals that at room temperature, coverages up to a monolayer exist, with the molecules engaged in metal carbene bonds. On all three surfaces, we resolve similar arrangements, which can be interpreted only in terms of mononuclear M(NHC) 2 (M = Cu, Ag, Au) complexes, reminiscent of the paired bonding of thiols to surface gold adatoms. Theoretical investigations for the case of Au unravel the charge distribution of a Au(111) surface covered by Au(NHC) 2 and reveal that this is the energetically preferential adsorption configuration.

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

    Directory of Open Access Journals (Sweden)

    Romaniuk Scott Nicholas

    2014-12-01

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

  20. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  1. Cobalt

    Science.gov (United States)

    Slack, John F.; Kimball, Bryn E.; Shedd, Kim B.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Cobalt is a silvery gray metal that has diverse uses based on certain key properties, including ferromagnetism, hardness and wear-resistance when alloyed with other metals, low thermal and electrical conductivity, high melting point, multiple valences, and production of intense blue colors when combined with silica. Cobalt is used mostly in cathodes in rechargeable batteries and in superalloys for turbine engines in jet aircraft. Annual global cobalt consumption was approximately 75,000 metric tons in 2011; China, Japan, and the United States (in order of consumption amount) were the top three cobalt-consuming countries. In 2011, approximately 109,000 metric tons of recoverable cobalt was produced in ores, concentrates, and intermediate products from cobalt, copper, nickel, platinum-group-element (PGE), and zinc operations. The Democratic Republic of the Congo (Congo [Kinshasa]) was the principal source of mined cobalt globally (55 percent). The United States produced a negligible amount of byproduct cobalt as an intermediate product from a PGE mining and refining operation in southeastern Montana; no U.S. production was from mines in which cobalt was the principal commodity. China was the leading refiner of cobalt, and much of its production came from cobalt ores, concentrates, and partially refined materials imported from Congo (Kinshasa).The mineralogy of cobalt deposits is diverse and includes both primary (hypogene) and secondary (supergene) phases. Principal terrestrial (land-based) deposit types, which represent most of world’s cobalt mine production, include primary magmatic Ni-Cu(-Co-PGE) sulfides, primary and secondary stratiform sediment-hosted Cu-Co sulfides and oxides, and secondary Ni-Co laterites. Seven additional terrestrial deposit types are described in this chapter. The total terrestrial cobalt resource (reserves plus other resources) plus past production, where available, is calculated to be 25.5 million metric tons. Additional resources of

  2. 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...

  3. A simple building-block route to (phosphanyl-carbene)palladium complexes via intermolecular addition of functionalised phosphanes to isocyanides

    NARCIS (Netherlands)

    Eberhard, M.R.; van Vliet, B.; Durán Páchon, L.; Rothenberg, G.; Eastham, G.; Kooijman, H.; Spek, A.L.; Elsevier, C.J.

    2009-01-01

    We present a straightforward protocol for making (phosphanyl-carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxy-carbene and a phosphane. The synthesis gives good yields (typically 70-90 %) for a variety of complexes (22 compounds). Moreover, it

  4. Auranofin and N-heterocyclic carbene gold-analogs are potent inhibitors of the bacteria Helicobacter pylori.

    Science.gov (United States)

    Owings, Joshua P; McNair, Nina N; Mui, Yiu Fung; Gustafsson, Tomas N; Holmgren, Arne; Contel, Maria; Goldberg, Joanna B; Mead, Jan R

    2016-07-01

    Auranofin is an FDA-approved gold-containing compound used for the treatment of rheumatoid arthritis. Recent reports of antimicrobial activity against protozoa and bacteria indicate that auranofin targets the reductive enzyme thioredoxin reductase (TrxR). We evaluated auranofin as well as five auranofin analogs containing N-heterocyclic carbenes (instead of the triethylphosphane present in auranofin) and five gold-carbene controls for their ability to inhibit or kill Helicobacter pylori in vitro Auranofin completely inhibited bacterial growth at 1.2 μM. Purified H. pylori TrxR was inhibited by auranofin in a cell-free assay (IC50 ∼88 nM). The most active gold(I)-N-heterocyclic carbene compounds exhibited MICs comparable to auranofin against H. pylori (2 μM), while also exhibiting lower toxicities for human embryonic kidney cells (HEK-293T cells). Median toxic concentrations (TC50) were 13-20-fold higher compared to auranofin indicating that they were less cytotoxic. The N-heterocyclic carbene analogs maybe well tolerated, but further evaluation is needed in vivo Finally, auranofin was synergistic with the antibiotic amoxicillin, suggesting that targeting both the reductive enzyme TrxR and cell wall synthesis may be effective against H. pylori infections. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  5. Cobalt oxide polymorph growth on electrostatic self-assembled nanoparticle arrays for dually tunable nano-textures

    International Nuclear Information System (INIS)

    Bulliard, Xavier; Benayad, Anass; Lee, Kwang-Hee; Choi, Yun-Hyuk; Lee, Jae Cheol; Park, Jong-Jin; Kim, Jong-Min

    2011-01-01

    We report on a method for surface nano-texturing on a plastic substrate. Nano-objects with a silica nanoparticle core and a textured cobalt oxide crown are created with selectable density on the plastic substrate. The resulting dual morphology is easily tuned over large areas, either by changing the parameters directing nanoparticle deposition through electrostatic self-arrangement for nano-object density control, or the parameter directing cobalt oxide deposition for shape control. The entire process takes place at room temperature, with no chemicals harmful to the plastic substrate. The ready modulation of the dual morphology is used to control the wettability properties of the plastic film, which is covered by nano-objects.

  6. Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

    Science.gov (United States)

    Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

    2011-01-01

    The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

  7. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  8. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi

    2016-01-01

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise

  9. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    KAUST Repository

    Kim, Hye Kyung

    2017-04-12

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  10. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    KAUST Repository

    Kim, Hye Kyung; Hyla, Alexander; Winget, Paul; Li, Hong; Wyss, Chelsea M.; Jordan, Abraham J.; Larrain, Felipe A.; Sadighi, Joseph P.; Fuentes-Hernandez, Canek; Kippelen, Bernard; Bredas, Jean-Luc; Barlow, Stephen; Marder, Seth R.

    2017-01-01

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  11. N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

    KAUST Repository

    Guo, Hao

    2015-11-16

    An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

  12. N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

    KAUST Repository

    Guo, Hao; Xing, Fen; Du, Guang-Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

    2015-01-01

    An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

  13. Facile insertion of a cyclic alkyl(amino) carbene carbon into the B-B bond of diboron(4) reagents.

    Science.gov (United States)

    Eichhorn, Antonius F; Kuehn, Laura; Marder, Todd B; Radius, Udo

    2017-10-24

    We report herein the room temperature insertion of the carbene carbon atom of the cyclic (alkyl)(amino) carbene cAAC Me into the B-B single bonds of the diboron(4) compounds B 2 pin 2 , B 2 cat 2 , B 2 neop 2 , and B 2 eg 2 (pin = pinacolato, cat = catecholato, neop = neopentylglycolato, eg = ethyleneglycolato).

  14. Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

    Energy Technology Data Exchange (ETDEWEB)

    Wienand, A.; Reissig, H.U. (Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany))

    1990-12-01

    The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

  15. Adsorbate-driven cooling of carbene-based molecular junctions

    Czech Academy of Sciences Publication Activity Database

    Foti, Giuseppe; Vázquez, Héctor

    2017-01-01

    Roč. 8, Oct (2017), s. 2060-2068 ISSN 2190-4286 R&D Projects: GA ČR GA15-19672S EU Projects: European Commission(XE) 702114 - HEATEXMOL Institutional support: RVO:68378271 Keywords : adsorbate * carbene * current-induced heating and cooling * molecular junction * vibrations Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.127, year: 2016

  16. Inserção C-H de carbenóides de ródio em água e reutilização do catalisador Rhodium (II carbene C-H insertion in water and catalyst reuse

    Directory of Open Access Journals (Sweden)

    Nuno R. Candeias

    2007-01-01

    Full Text Available A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonylacetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh2(OAc4. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization.

  17. N-Heterocyclic carbene functionalized goup 7-9 transition metal

    NARCIS (Netherlands)

    Aktas, H.; Slootweg, J.C.; Ehlers, A.W.; Lutz, M.; Spek, A.L.; Lammertsma, K.

    2009-01-01

    The N-heterocyclic carbene (NHC) functionalized phosphinidene complexes [(pCy)(IiPr2Me2)- RudPMes*] (4), [(pCy)(IiPr2Me2)OsdPMes*] (6), and [(Cp*)(IiPr2Me2)RhdPMes*] (7) were generated by a double-dehydrohalogenation-ligation sequence of the corresponding primary phosphine complexes with 3 equiv of

  18. 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.

  19. Effect of two kinds of porcelain crown on AST, ALP, TNF-α, IL-8, GP-x and MDA levels in gingival crevicular fluid

    Directory of Open Access Journals (Sweden)

    Ya-Ling Wang

    2016-09-01

    Full Text Available Objective: To investigate the effect of two kinds of porcelain crown on AST, ALP, TNF-α, IL-8, GP-x and MDA levels in gingival crevicular fluid. Methods: A total of 80 patients with dental porcelain crowns at front teeth during February 2013 to February 2016 were randomly divided into cobalt-chromium alloy PFM group (n=40 and gold alloy PFM group (n=40. After 6 months, the amount of gingival crevicular fluid, GI, PD, AST, ALP, TNF-α, IL-8, GP-x and MDA levels in gingival crevicular fluid were recorded and analyzed. Results: There were no differences in amount of gingival crevicular fluid, GI and PD before treatment of the two groups (P>0.05. After treatment, the amount of gingival crevicular fluid, GI and PD of the two groups were significantly higher than before treatment (P0.05. After treatment, the AST, ALP, TNF-α, IL-8 and MDA levels in gingival crevicular fluid of the two groups were significantly higher than before treatment (P<0.05, but that of the gold alloy PFM group were significantly lower than cobalt-chromium alloy PFM group (P<0.05. After treatment, the GP-x level in gingival crevicular fluid of the two groups were significantly lower than before treatment (P<0.05, but that of the gold alloy PFM group were significantly higher than cobalt-chromium alloy PFM group (P<0.05. Conclusions: Gold alloy PFM can significantly reduce the AST, ALP, TNF-α, IL-8 and MDA levels in gingival crevicular fluid, improve the GP-x level in gingival crevicular fluid, shows better biocompatibility and clinical outcomes than cobalt-chromium alloy PFM.

  20. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    KAUST Repository

    El-Batta, Amer; Waltman, Andrew W.; Grubbs, Robert H.

    2011-01-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis

  1. Reactivity of N-heterocyclic carbene-pyridine palladacyclopentadiene complexes toward halogen addition. The unpredictable course of the reaction.

    Science.gov (United States)

    Visentin, Fabiano; Santo, Claudio; Scattolin, Thomas; Demitri, Nicola; Canovese, Luciano

    2017-08-08

    As an extension of a previously published work we have reacted some palladacyclopentadiene complexes stabilized by bidentate N-heterocyclic carbene-pyridine or monodentate N-heterocyclic carbene-pyridine and isocyanide ligands with the halogens I 2 and Br 2 . All the bidentate and monodentate complexes react with halogens to give at first the expected σ-coordinated butadienyl fragment. However, two of the less hindered NHC carbene-pyridine bidentate butadienyl iodo derivatives undergo a further rearrangement and novel Pd(ii) complexes characterized by a ten term coordinative ring were isolated and characterized. In the most favorable case we were able to carry out the kinetics of rearrangement and measure its reaction rate. Moreover, we have surmised a plausible mechanism on the basis of a dedicated computational approach and in one case the surprising structure characterized by the ten term coordinative ring was resolved by X-ray diffraction.

  2. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    International Nuclear Information System (INIS)

    Bertolino, María Candelaria; Granados, Alejandro Manuel

    2016-01-01

    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  3. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bertolino, María Candelaria, E-mail: cbertolino@fcq.unc.edu.ar; Granados, Alejandro Manuel, E-mail: ale@fcq.unc.edu.ar

    2016-10-15

    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  4. Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

    KAUST Repository

    Rieb, Julia

    2014-09-15

    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenethiophene)methane]iron(II) hexafluorophosphate (2b) were obtained by aminolysis of [Fe{N(SiMe3)2}2(THF)] with furan- and thiophene-functionalized bis(imidazolium) salts 1a and 1b in acetonitrile. The SC-XRD structures of 2a and 2b show coordination of the bis(carbene) ligand in a bidentate fashion instead of a possible tetradentate coordination. The four other coordination sites of these distorted octahedral complexes are occupied by acetonitrile ligands. Crystallization of 2a in an acetone solution by the slow diffusion of Et2O led to the formation of cisdiacetonitriledi[ bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (3a) with two bis(carbene) ligands coordinated in a bidentate manner and two cis-positioned acetonitrile molecules. Compounds 2a and 2b are the first reported iron(II) carbene complexes with four coordination sites occupied by solvent molecules, and it was demonstrated that those solvent ligands can undergo ligand-exchange reactions.

  5. Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions.

    Science.gov (United States)

    Wolf, Matthew W; Vargas, David A; Lehnert, Nicolai

    2017-05-15

    The small, stable heme protein myoglobin (Mb) was modified through cofactor substitution and mutagenesis to develop a new catalyst for carbene transfer reactions. The native heme was removed from wild-type Mb and several Mb His64 mutants (H64D, H64A, H64V), and the resulting apoproteins were reconstituted with ruthenium mesoporphyrin IX (RuMpIX). The reconstituted proteins (RuMb) were characterized by UV-vis and circular dichroism spectroscopy and were used as catalysts for the N-H insertion of aniline derivatives and the cyclopropanation of styrene derivatives. The best catalysts for each reaction were able to achieve turnover numbers (TON) up to 520 for the N-H insertion of aniline, and 350 TON for the cyclopropanation of vinyl anisole. Our results show that RuMb is an effective catalyst for N-H insertion, with the potential to further increase the activity and stereoselectivity of the catalyst in future studies. Compared to native Mb ("FeMb"), RuMb is a more active catalyst for carbene transfer reactions, which leads to both heme and protein modification and degradation and, hence, to an overall much-reduced lifetime of the catalyst. This leads to lower TONs for RuMb compared to the iron-containing analogues. Strategies to overcome this limitation are discussed. Finally, comparison is also made to FeH64DMb and FeH64AMb, which have not been previously investigated for carbene transfer reactions.

  6. Rare-earth- and uranium-mesoionic carbenes. A new class of f-block carbene complex derived from an N-heterocyclic olefin

    Energy Technology Data Exchange (ETDEWEB)

    Seed, John A.; Gregson, Matthew; Chilton, Nicholas F.; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom)

    2017-09-11

    Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found in the free form or ligated to only a few d-block ions. Unprecedented f-block MIC complexes [M(N''){sub 3}{CN(Me)C(Me)N(Me)CH}] (M=U, Y, La, Nd; N''=N(SiMe{sub 3}){sub 2}) are reported. These complexes were prepared by a formal 1,4-proton migration reaction when the metal triamides [M(N''){sub 3}] were treated with the N-heterocyclic olefin H{sub 2}C=C(NMeCH){sub 2}, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f{sup 3} uranium(III) complex suggest the presence of a U=C donor-acceptor bond, composed of a MIC→U σ-component and a U(5f)→MIC(2p) π-back-bond, but for the d{sup 0}f{sup 0} Y and La and 4f{sup 3} Nd congeners only MIC→M σ-bonding is found. Considering the generally negligible π-acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognizing MICs as potential π-acid ligands when coordinated to strongly reducing metals. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  7. Role of β-h elimination in rhodium-mediated carbene insertion polymerization

    NARCIS (Netherlands)

    Finger, M.; Reek, J.N.H.; de Bruin, B.

    2011-01-01

    The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

  8. Unusual solvation through both p-orbital lobes of a carbene carbon

    Energy Technology Data Exchange (ETDEWEB)

    Hadad, C. Z., E-mail: cacier.hadad@udea.edu.co [Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, A. A. 1226 Medellín (Colombia); Jenkins, Samantha [College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Flórez, Elizabeth [Departamento de Ciencias Básicas, Universidad de Medellín, Carrera 87 N° 30-65, Medellín (Colombia)

    2015-03-07

    As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

  9. Interfacial charge separation and photovoltaic efficiency in Fe(ii)-carbene sensitized solar cells.

    Science.gov (United States)

    Pastore, Mariachiara; Duchanois, Thibaut; Liu, Li; Monari, Antonio; Assfeld, Xavier; Haacke, Stefan; Gros, Philippe C

    2016-10-12

    The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(ii)-carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(ii)-NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(ii)-carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.

  10. Explicit role of dynamical and nondynamical electron correlation on singlet-triplet splitting in carbenes

    International Nuclear Information System (INIS)

    Seal, Prasenjit; Chakrabarti, Swapan

    2007-01-01

    Density functional theoretical studies have been performed on carbene systems to determine the singlet-triplet splitting and also to explore the role of electron correlation. Using an approximate method of separation of dynamical and nondynamical correlation, it is found that dynamical and nondynamical electron correlation stabilizes the singlet state relative to the triplet for halo carbenes in both BLYP and B3LYP methods. Calculations performed on higher homologues of methylene suggest that beyond CH(CH 3 ), both the electron correlations have leveling effect in stabilizing the singlet state relative to the triplet. It has also been observed while dynamical electron correlation fails to provide any substantial degree of stabilization to the singlet states of higher homologues of methylene in B3LYP method, an opposite trend is observed for nondynamical counterpart. Among the larger systems studied (9-triptycyl)(α-naphthyl)-carbene has the highest stability of the triplet state whereas bis-imidazol-2-ylidenes has the most stable singlet state. Interestingly, the values of the dynamical electron correlation for each state of each system studied are different for the two methods used. The reason behind this apparent discrepancy lies in the fact that the coefficients of the LYP part in B3LYP and BLYP functionals are different

  11. Synthesis of Backfunctionalized Imidazolinium Salts and NHC Carbene Complexes

    Science.gov (United States)

    2017-04-02

    Backfunctionalized Imidazolinium salts and NHC carbene complexes – Initial Research – Unintended Discovery – Survey chemistry of aromatic systems – Expansion of...survey chemistry to aliphatics • Conclusions and Future Directions Introduction 3 Distribution A: Approved for Public Release; Distribution Unlimited...AFRL – Tenant of Edwards AFB since late ‘50s – Full scale testing of the Atlas rockets (Gemini missions) – Initial testing of the F-1 engine (Apollo

  12. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

    KAUST Repository

    Rouen, Mathieu

    2014-09-11

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

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

    Science.gov (United States)

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

    2013-01-01

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

  14. Tip-induced gating of molecular levels in carbene-based junctions

    Czech Academy of Sciences Publication Activity Database

    Foti, Giuseppe; Vázquez, Héctor

    2016-01-01

    Roč. 27, č. 12 (2016), 1-8, č. článku 125702. ISSN 0957-4484 R&D Projects: GA ČR GA15-19672S Institutional support: RVO:68378271 Keywords : single molecule transport * N-heterocyclic carbene * tip-induced gating * DFT-NEGF * metal-molecule charge rearrangement Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.440, year: 2016

  15. A theobromine derived silver N-heterocyclic carbene: synthesis, characterization, and antimicrobial efficacy studies on cystic fibrosis relevant pathogens†

    Science.gov (United States)

    Panzner, Matthew J.; Hindi, Khadijah M.; Wright, Brian D.; Taylor, Jane B.; Han, Daniel S.

    2009-01-01

    The increasing incidence of multidrug-resistant (MDR) pulmonary infections in the cystic fibrosis (CF) population has prompted the investigation of innovative silver based therapeutics. The functionalization of the naturally occurring xanthine theobromine at the N1 nitrogen atom with an ethanol substituent followed by the methylation of the N9 nitrogen atom gives the N-heterocyclic carbene precursor 1-(2-hydroxyethyl)-3,7,9-trimethylxanthinium iodide. The reaction of this xanthinium salt with silver acetate produces the highly hydrophilic silver carbene complex SCC8. The in vitro antimicrobial efficacy of this newly synthesized complex was evaluated with excellent results on a variety of virulent and MDR pathogens isolated from CF patients. A comparative in vivo study between the known caffeine derived silver carbene SCC1 and SCC8 demonstrated the ability of both complexes to improve the survival rates of mice in a pneumonia model utilizing the clinically isolated infectious strain of Pseudomonas aeruginosa PA M57-15. PMID:20449175

  16. A theobromine derived silver N-heterocyclic carbene: synthesis, characterization, and antimicrobial efficacy studies on cystic fibrosis relevant pathogens.

    Science.gov (United States)

    Panzner, Matthew J; Hindi, Khadijah M; Wright, Brian D; Taylor, Jane B; Han, Daniel S; Youngs, Wiley J; Cannon, Carolyn L

    2009-09-21

    The increasing incidence of multidrug-resistant (MDR) pulmonary infections in the cystic fibrosis (CF) population has prompted the investigation of innovative silver based therapeutics. The functionalization of the naturally occurring xanthine theobromine at the N(1) nitrogen atom with an ethanol substituent followed by the methylation of the N(9) nitrogen atom gives the N-heterocyclic carbene precursor 1-(2-hydroxyethyl)-3,7,9-trimethylxanthinium iodide. The reaction of this xanthinium salt with silver acetate produces the highly hydrophilic silver carbene complex SCC8. The in vitro antimicrobial efficacy of this newly synthesized complex was evaluated with excellent results on a variety of virulent and MDR pathogens isolated from CF patients. A comparative in vivo study between the known caffeine derived silver carbene SCC1 and SCC8 demonstrated the ability of both complexes to improve the survival rates of mice in a pneumonia model utilizing the clinically isolated infectious strain of Pseudomonas aeruginosa PA M57-15.

  17. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  18. Recovery of Cobalt as Cobalt Oxalate from Cobalt Tailings Using Moderately Thermophilic Bioleaching Technology and Selective Sequential Extraction

    Directory of Open Access Journals (Sweden)

    Guobao Chen

    2016-07-01

    Full Text Available Cobalt is a very important metal which is widely applied in various critical areas, however, it is difficult to recover cobalt from minerals since there is a lack of independent cobalt deposits in nature. This work is to provide a complete process to recover cobalt from cobalt tailings using the moderately thermophilic bioleaching technology and selective sequential extraction. It is found that 96.51% Co and 26.32% Cu were extracted after bioleaching for four days at 10% pulp density. The mean compositions of the leach solutions contain 0.98 g·L−1 of Co, 6.52 g·L−1 of Cu, and 24.57 g·L−1 of Fe (III. The copper ion was then recovered by a solvent extraction process and the ferric ions were selectively removed by applying a goethite deironization process. The technological conditions of the above purification procedures were deliberately discussed. Over 98.6% of copper and 99.9% of ferric ions were eliminated from the leaching liquor. Cobalt was finally produced as cobalt oxalate and its overall recovery during the whole process was greater than 95%. The present bioleaching process of cobalt is worth using for reference to deal with low-grade cobalt ores.

  19. Amide Synthesis from Alcohols and Amines Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Osztrovszky, Gyorgyi; Nordstrøm, Lars Ulrik Rubæk

    2010-01-01

    The direct synthesis of amides from alcohols and amines is described with the simultaneous liberation of dihydrogen. The reaction does not require any stoichiometric additives or hydrogen acceptors and is catalyzed by ruthenium N-heterocyclic carbene complexes. Three different catalyst systems...... are presented that all employ 1,3-diisopropylimidazol-2-ylidene (IiPr) as the carbene ligand. In addition, potassium tert-butoxide and a tricycloalkylphosphine are required for the amidation to proceed. In the first system, the active catalyst is generated in situ from [RuCl2(cod)] (cod = 1,5-cyclooctadiene), 1...... chloride and base. A range of different primary alcohols and amines have been coupled in the presence of the three catalyst systems to afford the corresponding amides in moderate to excellent yields. The best results are obtained with sterically unhindered alcohols and amines. The three catalyst systems do...

  20. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    International Nuclear Information System (INIS)

    Ramesh, Thimmasandra Narayan

    2010-01-01

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co 3 O 4 . The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co 3 O 4 phase.

  1. Late metal carbene complexes generated by multiple C-H activations: examining the continuum of M=C bond reactivity.

    Science.gov (United States)

    Whited, Matthew T; Grubbs, Robert H

    2009-10-20

    Unactivated C(sp(3))-H bonds are ubiquitous in organic chemicals and hydrocarbon feedstocks. However, these resources remain largely untapped, and the development of efficient homogeneous methods for hydrocarbon functionalization by C-H activation is an attractive and unresolved challenge for synthetic chemists. Transition-metal catalysis offers an attractive possible means for achieving selective, catalytic C-H functionalization given the thermodynamically favorable nature of many desirable partial oxidation schemes and the propensity of transition-metal complexes to cleave C-H bonds. Selective C-H activation, typically by a single cleavage event to produce M-C(sp(3)) products, is possible through myriad reported transition-metal species. In contrast, several recent reports have shown that late transition metals may react with certain substrates to perform multiple C-H activations, generating M=C(sp(2)) complexes for further elaboration. In light of the rich reactivity of metal-bound carbenes, such a route could open a new manifold of reactivity for catalytic C-H functionalization, and we have targeted this strategy in our studies. In this Account, we highlight several early examples of late transition-metal complexes that have been shown to generate metal-bound carbenes by multiple C-H activations and briefly examine factors leading to the selective generation of metal carbenes through this route. Using these reports as a backdrop, we focus on the double C-H activation of ethers and amines at iridium complexes supported by Ozerov's amidophosphine PNP ligand (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)), allowing isolation of unusual square-planar iridium(I) carbenes. These species exhibit reactivity that is distinct from the archetypal Fischer and Schrock designations. We present experimental and theoretical studies showing that, like the classical square-planar iridium(I) organometallics, these complexes are best described as nucleophilic at iridium. We discuss

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

    Science.gov (United States)

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

    2015-01-01

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

  3. Blood doping by cobalt. Should we measure cobalt in athletes?

    Directory of Open Access Journals (Sweden)

    Guidi Gian

    2006-07-01

    Full Text Available Abstract Background Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Presentation of the hypothesis Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Testing the hypothesis Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Implications of the hypothesis Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice

  4. Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

    Science.gov (United States)

    Wentrup, Curt

    2011-06-21

    Rearrangements of aromatic and heteroaromatic nitrenes and carbenes can be initiated with either heat or light. The thermal reaction is typically induced by flash vacuum thermolysis, with isolation of the products at low temperatures. Photochemical experiments are conducted either under matrix isolation conditions or in solution at ambient temperature. These rearrangements are usually initiated by ring expansion of the nitrene or carbene to a seven-membered ring ketenimine, carbodiimide, or allene (that is, a cycloheptatetraene or an azacycloheptatetraene when a nitrogen is involved). Over the last few years, we have found that two types of ring opening take place as well. Type I is an ylidic ring opening that yields nitrile ylides or diazo compounds as transient intermediates. Type II ring opening produces either dienylnitrenes (for example, from 2-pyridylnitrenes) or 1,7-(1,5)-diradicals (such as those formed from 2-quinoxalinylnitrenes), depending on which of these species is better stabilized by resonance. In this Account, we describe our achievements in elucidating the nature of the ring-opened species and unraveling the connections between the various reactive intermediates. Both of these ring-opening reactions are found, at least in some cases, to dominate the subsequent chemistry. Examples include the formation of ring-opened ketenimines and carbodiimides, as well as the ring contraction reactions that form five-membered ring nitriles (such as 2- and 3-cyanopyrroles from pyridylnitrenes, N-cyanoimidazoles from 2-pyrazinyl and 4-pyrimidinylnitrenes, N-cyanopyrazoles from 2-pyrimidinylnitrenes and 3-pyridazinylnitrenes, and so forth). The mechanisms of formation of the open-chain and ring-contraction products were unknown at the onset of this study. In the course of our investigation, several reactions with three or more consecutive reactive intermediates have been unraveled, such as nitrene, seven-membered cyclic carbodiimide, and open-chain nitrile ylide

  5. Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

    Science.gov (United States)

    Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

    Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

  6. A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO4(C(OMeMe

    Directory of Open Access Journals (Sweden)

    Tareq Irshaidat

    2010-01-01

    Full Text Available Fischer carbenes are important starting materials for C-C bond formation via coupling reactions between carbene and wide variety of substituted alkenes or alkynes. This DFT study shed light on unique fundamental organic/organometallic aspects for the C(OMeMe carbene in the free form and in case of bonding with M(CO4 (M= Cr, Mo, W. The data illustrate that the structures of the title intermediates include a unique structure stabilizing intramolecular M…C-H interaction (agostic interaction. This conclusion was made based on calculated NMR data (for carbon and hydrogen, structural parameters, energy calculations of conformers (C-C conformation, selected IR stretching frequencies (C-O, C-C, and C-H, and atomic charges. The agostic interaction is most efficient in case of chromium and in general is described as an overlap between the σ-bond electron pair of C-H with an empty d-orbital of the metal. These characterized examples are new addition to the orbital interaction theory.

  7. Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

    Science.gov (United States)

    Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

    2015-10-26

    Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dirhodium(II Carbenes : The Chiral Product Cascade

    Directory of Open Access Journals (Sweden)

    Gregory H. P. Roos

    2000-12-01

    Full Text Available The last decade has witnessed enormous growth in the spectrum of highly efficient asymmetric synthetic transformations. One prominent example of this progress is the application of dirhodium (II carbenes generated from diazo- precursors. Innovative construction of ‘designer’ catalysts has played a integral role in extending the breadth of the synthetic cascade of non-racemic products now available through the range of cyclopropanation, C-X insertion, aromatic cycloaddition-rearrangement, and ylide-based reaction types. This review deals briefly with an overview of the important catalytic systems and maintains as its primary focus the cascade of diverse optically enriched products that flow from their applications.

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

    Directory of Open Access Journals (Sweden)

    Geeta Maruti Doodamani

    2011-01-01

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

  10. Cyclometalated N-heterocyclic carbene iridium(iii) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds.

    Science.gov (United States)

    Lanoë, Pierre-Henri; Chan, Jonny; Groué, Antoine; Gontard, Geoffrey; Jutand, Anny; Rager, Marie-Noelle; Armaroli, Nicola; Monti, Filippo; Barbieri, Andrea; Amouri, Hani

    2018-03-06

    A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C^N) 2 (C^C:)] has been prepared. Two sets of compounds were designed, those where (C^C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C^N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C^C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C^N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a,b were also prepared and fully characterized. The N-heterocyclic carbene Ir(iii) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(iii) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from 3 MLCT to 3 LC, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k nr values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

  11. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura

    2016-12-26

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise surprising experimental results. In this review, the main conclusions from recent literature are discussed, with the aim to offer a vision of the potential of theoretical analyses of NMR properties.

  12. Cobalt release from inexpensive jewellery

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten Stendahl; Menné, Torkil

    2010-01-01

    . Conclusions: This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future......Objectives: The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. Methods: The cobalt spot test was used to assess cobalt release from all items...

  13. Carbene Chemistry. I. Stereochemical Integrity at C Alpha in Ketone Tosylhydrazones. II. Hydrogen Migration in 2-Carbena-6,6-Dimethylnorbornane.

    Science.gov (United States)

    1978-02-01

    H20, 10% Na2 CO3 , H20, and dried over MqSO 4 . Yields were typically ca. 75%. "! 33 CARBENE CHEMISTRY PART II. HYDROGEN MIGRATION IN 2-CARBENA-6,6...any a delocaliza- tion. Thus if one assumes a single product determining intermediate, carbene 54 is classical in the usual sense of the word. It has...placed in a refrigerator. The crystalline product was re- crystallized from methanol-O-d/D20 yielding purified tosylhydrazone with mp 156-1580. 58

  14. Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

    DEFF Research Database (Denmark)

    Makarov, Ilya; Fristrup, Peter; Madsen, Robert

    2012-01-01

    The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

  15. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    Science.gov (United States)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil; Lidén, Carola; Julander, Anneli; Møller, Per; Johansen, Jeanne Duus

    2010-08-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure. The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. The cobalt spot test was used to assess cobalt release from all items. Microstructural characterization was made using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). Cobalt release was found in 4 (1.1%) of 354 items. All these had a dark appearance. SEM/EDS was performed on the four dark appearing items which showed tin-cobalt plating on these. This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future. Industries may not be fully aware of the potential cobalt allergy problem.

  16. A facile route to ruthenium-carbene complexes and their application in furfural hydrogenation

    NARCIS (Netherlands)

    Strassberger, Z.; Mooijman, M.; Ruijter, E.; Alberts, A.H.; de Graaff, C.; Orru, R.V.A.; Rothenberg, G.

    2010-01-01

    A number of new N-heterocyclic carbene (NHC) ligands were synthesized via a multicomponent reaction, wherein an aldehyde or ketone, a primary amine and an α-acidic isocyanide were reacted, giving the corresponding 2H-2-imidazolines. These were easily alkylated with an alkyl halide at position N-3,

  17. Cobalt

    International Nuclear Information System (INIS)

    Stolyarova, I.A.; Bunakova, N.Yu.

    1983-01-01

    The neutron-activation method for determining cobalt in rocks, polymetallic and iron ores and rockforming minerals at 2x10 -6 -5x10 -3 % content is developed. Cobalt determination is based on the formation under the effect of thermal neutrons of nuclear reactor of the 60 Co radioactive isotope by the 59 Co (n, γ) 60 Co reaction with radiation energy of the most intensive line of 1333 keV. Cobalt can be determined by the scheme of the multicomponent analysis from the sample with other elements. Co is determined in the solution after separation of all determinable by the scheme elements. The 60 Co intensity is measured by the mUltichannel gamma-spectrometer with Ge(Li)-detector

  18. Application of Chan-Lam cross coupling for the synthesis of N-heterocyclic carbene precursors bearing strong electron donating or withdrawing groups

    Science.gov (United States)

    Huang, Liliang; He, Chengxiang; Sun, Zhihua

    2015-07-01

    Chan-Lam cross coupling allowed efficient synthesis of N,N’-disubstituted ortho-phenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with moderate to high yields. These diamines can then be turned into N-heterocyclic carbene precursors after condensation with trimethyl orthoformate. The same strategy can also be utilized for the synthesis of N-monosubstituted aniline derivatives containing a functionalized ortho-aminomethyl group as intermediates for chiral 6-membered ring carbene precursors.

  19. Cobalt release from implants and consumer items and characteristics of cobalt sensitized patients with dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Menne, Torkil; Liden, Carola

    2012-01-01

    -containing dental alloys and revised hip implant components.Results. Six of eight dental alloys and 10 of 98 revised hip implant components released cobalt in the cobalt spot test, whereas none of 50 mobile phones gave positive reactions. The clinical relevance of positive cobalt test reactions was difficult......-tested dermatitis patients in an attempt to better understand cobalt allergy.Materials and methods. 19 780 dermatitis patients aged 4-99 years were patch tested with nickel, chromium or cobalt between 1985 and 2010. The cobalt spot test was used to test for cobalt ion release from mobile phones as well as cobalt...

  20. Actinide/crown ether chemistry

    International Nuclear Information System (INIS)

    Benning, M.M.

    1988-01-01

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

  1. Is There a Correlation Between Tensile Strength and Retrievability of Cemented Implant-Retained Crowns Using Artificial Aging?

    Science.gov (United States)

    Mehl, Christian; Ali, Shurouk; El Bahra, Shadi; Harder, Sönke; Vollrath, Oliver; Kern, Matthias

    2016-01-01

    The main goal of this in-vitro study was to evaluate whether tensile strength and retrievability of cemented implant-retained crowns correlate when using artificial aging. A total of 128 crowns were fabricated from a cobalt-chromium alloy for 128 tapered titanium abutments (6 degrees taper, 4.3 mm diameter, 4 mm length, Camlog). The crowns were cemented with glass-ionomer (Ketac Cem, 3M) or resin cements (Multilink Implant, Telio CS Cem [Ivoclar Vivadent], Retrieve [Parkell]). Multilink Implant was used without priming. The experimental groups were subjected to either 37,500 thermal cycles between 5°C and 55°C, 1,200,000 chewing cycles, or a combination of both. Control groups were stored for 10 days in deionized water. The crowns were removed with a universal testing machine or a clinically used removal device (Coronaflex, KaVo). Data were statistically analyzed using nonparametrical tests. Retention values were recorded between 31 N and 362 N. Telio CS Cem showed the lowest retention values, followed by Retrieve, Ketac Cem, and Multilink Implant (P≤.0001). The number of removal attempts with the Coronaflex were not significantly different between the cements (P>.05). Thermal cycling and chewing simulation significantly influenced the retrieval of Retrieve Telio CS Cem, and Ketac Cem specimens (P≤.05). Only for Multilink Implant and Telio CS Cem correlations between removal with the universal testing machine and the Coronaflex could be revealed (P≤.0001). Ketac Cem and Multilink Implant (without silane) can be used for a semipermanent cementation. Retrieve and Telio CS Cem are recommendable for a temporary cementation.

  2. Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

    KAUST Repository

    Queval, Pierre

    2013-12-04

    A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Pull-push mechanism for the 1,2-hydrogen rearrangement of carbenes. Substituent and deuterium isotope effects for thermal decomposition of 1-phenyl-2-diazopropanes

    International Nuclear Information System (INIS)

    Su, D.T.T.; Thornton, E.R.

    1978-01-01

    Intramolecular and intermolecular deuterium isotope effects have been measured for the thermal carbene H rearrangements of three substituted 1-phenyl-2-diazopropanes-1-d in hexane at 25 0 C. The isotope effects, k/sub H//k/sub D/, vary from ca. 1.2 to 1.5, increasing with electron-withdrawing substituents, for the formation of both cis- and trans-β-methylstyrenes. Product ratios were determined for these compounds as well as the corresponding undeuterated ones, permitting calculation of intermolecular primary and secondary isotope effects. In addition, the competition among the cis and trans products and the product of H migration from the terminal methyl group permitted determination of Hammett rho values of ca. -1 for the competition between benzylic and terminal migration. The results strongly indicate a ''pull-push'' mechanism, which can be pictured roughly as electrophilic attack on the C--H bond by the phantom p orbital of the carbene along with backside nucleophilic attack by the carbene unshared electron pair to push the H away and form the π bond. The data are believed to be consistent only with a nonzero barrier for the carbene hydrogen rearrangement

  4. Role of carbene complexes in initiation and chain propagation in double bond redistribution reactions

    International Nuclear Information System (INIS)

    Dolgoplosk, K.L.; Makovetskij, E.I.; Tinyakova, E.I.; Golenko, T.G.; Oreshkin, I.A.

    1976-01-01

    A study has been made of the role of carbene complexes of tungsten in initiation and propagation of the ring-opening polymerization of cycloolefins. Data are given on polymerization of cyclopentene and cycloocterdiene-1,5 in the presence of the system tungsten chloride-diazo-compound (DAC)

  5. Enantioselective N-Heterocyclic Carbene Catalysis via the Dienyl Acyl Azolium.

    Science.gov (United States)

    Gillard, Rachel M; Fernando, Jared E M; Lupton, David W

    2018-04-16

    Herein we report the enantioselective N-heterocyclic carbene catalyzed (4+2) annulation of the dienyl acyl azolium with enolates. The reaction exploits readily accessible acyl fluorides and TMS enol ethers to give a range of highly enantio- and diastereo-enriched cyclohexenes (most >97:3 er and >20:1 dr). The reaction was found to require high nucleophilicity NHC catalysts with mechanistic studies supporting a stepwise 1,6-addition/β-lactonization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. Asymmetric Reduction of tert-Butanesulfinyl Ketimines by N-Heterocyclic Carbene Boranes.

    Science.gov (United States)

    Liu, Tao; Chen, Ling-yan; Sun, Zhihua

    2015-11-20

    N-heterocyclic carbene borane (NHC-borane) based on a triazole core is demonstrated for the first time to be efficient for reduction of a variety of tert-butanesulfinyl ketimines. Up to 95% yield and up to >99% diastereomeric excess were achieved. NHC-borane exhibited excellent activities that are more efficient than or comparable to commonly used reductive reagents such as NaBH4, NaBH3CN, l-selectride, Ru catalyst, or BH3-THF.

  8. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando

    2015-09-30

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  9. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando; Lazreg, Faï ma; Minenkov, Yury; Cavallo, Luigi; Cazin, Catherine S. J.

    2015-01-01

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  10. Bimacrocyclic concave N-heterocyclic carbenes (NHCs): synthesis, structure, and application in catalyses

    OpenAIRE

    Lüning , Ulrich; Winkelmann , Ole

    2009-01-01

    Abstract Imidazolinium moieties have been incorporated into bimacrocycles to generate precursors for concave N-heterocyclic carbenes (NHCs). Starting from 2-nitroresorcinol and alkenols, symmetric concave imidazolinium salts 1 were obtained. Bimacrocyclization was achieved via ring closing metathesis (RCM). In an analogous fashion, axially chiral concave imidazolinium salts 2 were obtained by using a naphthalene bridgehead devoid of local C2-symmetry. The concave NHCs derived from ...

  11. Passivation and corrosion behaviours of cobalt and cobalt-chromium-molybdenum alloy

    International Nuclear Information System (INIS)

    Metikos-Hukovic, M.; Babic, R.

    2007-01-01

    Passivation and corrosion behaviour of the cobalt and cobalt-base alloy Co30Cr6Mo was studied in a simulated physiological solution containing chloride and bicarbonate ions and with pH of 6.8. The oxido-reduction processes included solid state transformations occurring at the cobalt/electrolyte interface are interpreted using theories of surface electrochemistry. The dissolution of cobalt is significantly suppressed by alloying it with chromium and molybdenum, since the alloy exhibited 'chromium like' passivity. The structural and protective properties of passive oxide films formed spontaneously at the open circuit potential or during the anodic polarization were studied using electrochemical impedance spectroscopy in the wide frequency range

  12. Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

    KAUST Repository

    Rieb, Julia; Raba, Andreas; Haslinger, Stefan; Kaspar, Manuel; Pö thig, Alexander; Cokoja, Mirza; Basset, Jean-Marie; Kü hn, Fritz

    2014-01-01

    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance

  13. Elicitation threshold of cobalt chloride

    DEFF Research Database (Denmark)

    Fischer, Louise A; Johansen, Jeanne D; Voelund, Aage

    2016-01-01

    : On the basis of five included studies, the ED10 values of aqueous cobalt chloride ranged between 0.0663 and 1.95 µg cobalt/cm(2), corresponding to 30.8-259 ppm. CONCLUSIONS: Our analysis provides an overview of the doses of cobalt that are required to elicit allergic cobalt contactdermatitis in sensitized...

  14. 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

  15. Quantum and Statistical Mechanics Applied to Singlet Carbenes, Pericyclic Reactions, and Condensed Phase Phenomena

    Science.gov (United States)

    Evanseck, Jeffrey Donald

    The completed research covers a broad range of theoretical applications in organic chemistry. It is divided into three chapters which covers the chemistry of singlet carbenes (Chapter 1), substituent effects in pericyclic rearrangements (Chapter 2), and the effects of solvent on the reactivity of organic reactions (Chapter 3). The selectivity between 1,2- and 1,4-intramolecular additions to restricted diene systems has been investigated. A decrease in activation energy for the intramolecular cycloaddition is noted for systems which approach the idealized geometry found with intermolecular addition of carbenes to olefins. Direct substitution at the carbene site dramatically effects the predicted activation barriers for 1,2-hydrogen shifts. An excellent correlation between the activation energy and a substituents sigma_sp {rm R}{rm o} parameters has been demonstrated. The long standing problem of orbital alignment influences on the selectivity of 1,2-hydrogen arrangements shows significant geometric distortions, yet has little influence on the rates of singlet alkylcarbene rearrangements. The exo-selectivities observed for 1,2-shifts in rigid systems are explained by torsional and steric interactions which develop in the transition structures. Substituent effects on pericyclic reactions have been computed for several conrotatory and disrotatory electrocyclizations. The six-electron disrotatory electrocyclization of 1-substituted hexatrienes displays a strong electronic component in determining stereoselectivity, despite incredible steric interference. The eight-electron conrotatory electrocyclization transition structure of 1-substituted octatetraene has an unusual helical transition structure which does not differentiate between substituent position. The effects of solvents on the acidity differences between E and Z esters has supplemented earlier ab initio quantum mechanical results on the enhanced acidity of Meldrum's acid. Monte Carlo simulations predict a

  16. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  17. 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...

  18. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    KAUST Repository

    Li, Shenyu; Kee, Choonwee; Huang, Kuo-Wei; Hor, Andy Sum Andy; Zhao, Jin

    2010-01-01

    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3

  19. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    KAUST Repository

    Wang, Ying; Du, Guang Fen; Xing, Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

    2015-01-01

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    KAUST Repository

    Wang, Ying

    2015-10-15

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Room-temperature hydrohydrazination of terminal alkynes catalyzed by saturated abnormal N-heterocyclic carbene-gold(I) complexes.

    Science.gov (United States)

    Manzano, Rubén; Wurm, Thomas; Rominger, Frank; Hashmi, A Stephen K

    2014-06-02

    A number of saturated abnormal N-heterocyclic carbene (NHC) complexes of gold, in combination with KBAr(F) 4 as activator, were successfully applied in the chemoselective addition of hydrazine to alkynes. The reaction proceeds even at room temperature, which was not possible to date with gold catalysts. The reaction can be applied to a number of substituted arylalkynes. With alkylalkynes the yields are low. The saturated abnormal NHC ligands are resistant to isomerization to the saturated normal NHC coordination mode under basic reaction conditions. Under acidic conditions, a simple protonation at the nitrogen atom not neighboring the carbene center was observed and unambiguously characterized by an X-ray crystal-structure analysis. Computational studies confirm that such an isomerization would be highly exothermic, the observed kinetic stability probably results from the need to shift two protons in such a process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of Fischer carbene complexes of iridium by C-H bond activation of methyl and cyclic ethers: Evidence for reversible {alpha}-hydrogen migration

    Energy Technology Data Exchange (ETDEWEB)

    Luecke, H.F.; Arndtsen, B.A.; Burger, P.; Bergman, R.G. [Lawrence Berkeley Lab., CA (United States)]|[Univ. of California, Berkeley, CA (United States)

    1996-03-13

    We report here a mild and versatile route to Fischer carbene complexes of iridium via the activation of C-H bonds of methyl and cyclic ethers, along with our preliminary studies of this rare family of carbene complexes. Theoretical studies suggest that {alpha}-hydrogen migrations can be kinetically favorable if a coordinatively unsaturated species can be accessed. Thus, the lability of the triflate ligand presumably facilitates this process. Further evidence for the rapidity, as well as reversibility, of this rearrangement was obtained by NMR analysis. 20 refs.

  3. Agricultural Crown Land in Saskatchewan

    International Nuclear Information System (INIS)

    Pyle, W.E.

    1998-01-01

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

  4. 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

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

    Science.gov (United States)

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

    2015-08-01

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

  6. Synthesis and crystal structure of the iridium(I) carbene complex with a pair of hydrogen wing tips

    Energy Technology Data Exchange (ETDEWEB)

    Huang, H.-Y.; Chen, Z.-M.; Wang, Y.; Wu, E.-M.; Wang, G. [Jiangsu Institute of Nuclear Medicine, Ministry of Health, Key Laboratory of Molecular Nuclear Medicine (China); Jiang, M.-J., E-mail: jmj16888@126.com [Nanjing Medical University, Affiliated Wuxi Peoples Hospital, Wuxi Institute of Translational Medicine, Department of Clinical Laboratory Science (China)

    2016-12-15

    The iridium(I) cyclooctadiene complex with two (3-tert-butylimidazol-2-ylidene) ligands [(H-Im{sup t}Bu){sub 2}Ir(COD)]{sup +}PF{sub 6}{sup −} (C{sub 22}H{sub 32}PF{sub 6}IrN{sub 4}) has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal atom, which is coordinated by two H-Im{sup t}Bu ligands and one cyclooctadiene group. The new iridium carbene complex has a pair of hydrogen wing tips. The Ir−C{sub carbene} bond lengths are 2.066(5) and 2.052(5) Å, and the bond angle C−Ir−C between these bonds is 95.54(19)°. The dihedral angle between two imidazol-2-ylidene rings is 86.42°.

  7. C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

    Science.gov (United States)

    Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2017-06-01

    Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Rhodium (II) carbene C-H insertion in water and catalyst reuse; Insercao C-H de carbenoides de rodio em agua e reutilizacao do catalisador

    Energy Technology Data Exchange (ETDEWEB)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M. [Instituto Superior Tecnico, Lisboa (Portugal)]. E-mail: carlosafonso@ist.utl.pt

    2007-07-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh{sub 2}(OAc){sub 4}. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  10. 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...

  11. Optimized Syntheses of Cyclopentadienyl Nickel Chloride Compounds Containing "N"-Heterocyclic Carbene Ligands for Short Laboratory Periods

    Science.gov (United States)

    Cooke, Jason; Lightbody, Owen C.

    2011-01-01

    Experiments are described for the preparation of imidazolium chloride precursors to "N"-heterocyclic carbenes and their cyclopentadienyl nickel chloride derivatives. The syntheses have been optimized for second- and third-year undergraduate laboratories that have a maximum programmed length of three hours per week. The experiments are flexible and…

  12. Cobalt metabolism and toxicology—A brief update

    International Nuclear Information System (INIS)

    Simonsen, Lars Ole; Harbak, Henrik; Bennekou, Poul

    2012-01-01

    Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co 2+ ) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co 2+ ) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co 2+ ) have recently been proposed to be due to putative inhibition of Ca 2+ entry and Ca 2+ -signaling and competition with Ca 2+ for intracellular Ca 2+ -binding proteins. The tissue partitioning of cobalt (Co 2+ ) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow phase lasting several weeks, and

  13. 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.

  14. Simple building-block route to (Phosphanyl-carbene)palladium complexes via intermolecular addition of functionalised phosphanes to isocyanides

    NARCIS (Netherlands)

    Eberhard, M.R.; van Vliet, Bart; Durán Páchon, L.; Rothenberg, G.; Eastham, G.; Kooijman, H.; Spek, A.L.; Elsevier, C.J.

    2009-01-01

    We present a straightforward protocol for making (phosphanyl- carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxycarbene and a phosphane. The synthesis gives good yields (typically 70–90%) for a variety of complexes (22 compounds). Moreover, it

  15. Cobalt metabolism and toxicology-A brief update

    Energy Technology Data Exchange (ETDEWEB)

    Simonsen, Lars Ole, E-mail: LOSimonsen@dadlnet.dk; Harbak, Henrik; Bennekou, Poul

    2012-08-15

    Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co{sup 2+}) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co{sup 2+}) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co{sup 2+}) have recently been proposed to be due to putative inhibition of Ca{sup 2+} entry and Ca{sup 2+}-signaling and competition with Ca{sup 2+} for intracellular Ca{sup 2+}-binding proteins. The tissue partitioning of cobalt (Co{sup 2+}) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow

  16. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Energy Technology Data Exchange (ETDEWEB)

    Azib, H

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

  17. Digital photo monitoring for tree crown

    Science.gov (United States)

    Neil Clark; Sang-Mook Lee

    2007-01-01

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

  18. Cobalt accumulation and circulation by blackgum trees

    International Nuclear Information System (INIS)

    Thomas, W.A.

    1975-01-01

    Blackgum (Nyssa sylvatica Marsh.) trees accumulate far greater concentrations of cobalt in mature foliage than do other species on the same site (363 ppM in ash of blackgum, compared with about 3 ppM by mockernut hickory and about 1 ppM by red maple, tulip tree, and white oak). Cobalt concentrations in dormant woody tissues of blackgum also significantly exceed those in the other four species. Inoculation of six blackgums with 60 Co revealed that cobalt remains mobile in the trees for at least 3 years. Foliar concentrations of stable cobalt increase uniformly until senescence. In late August, foliage accounts for only 9 percent of total tree weight but 57 percent of total tree cobalt. Losses of cobalt from trees occur almost entirely by leaf abscission, and the loss rates of weight and cobalt from decomposing litter are similar. Retention of cobalt in the biologically active soil layers perpetuates zones of cobalt concentration created by this species in woodlands

  19. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Slack, J.; Norton, J.L.; Malkoske, G.R.

    2003-01-01

    MDS Nordion has been supplying cobalt-60 sources to industry for industrial and medical purposes since 1946. These cobalt-60 sources are used in many market and product segments. The major application is in the health care industry where irradiators are used to sterilize single use medical products. These irradiators are designed and built by MDS Nordion and are used by manufacturers of surgical kits, gloves, gowns, drapes and other medical products. The irradiator is a large shielded room with a storage pool for the cobalt-60 sources. The medical products are circulated through the shielded room and exposed to the cobalt-60 sources. This treatment sterilizes the medical products which can then be shipped to hospitals for immediate use. Other applications for this irradiation technology include sanitisation of cosmetics, microbial reduction of pharmaceutical raw materials and food irradiation. The cobalt-60 sources are manufactured by MDS Nordion in their Cobalt Operations Facility in Kanata. More than 75,000 cobalt-60 sources for use in irradiators have been manufactured by MDS Nordion. The cobalt-60 sources are double encapsulated in stainless steel capsules, seal welded and helium leak tested. Each source may contain up to 14,000 curies. These sources are shipped to over 170 industrial irradiators around the world. This paper will focus on the MDS Nordion proprietary technology used to produce the cobalt-60 isotope in CANDU reactors. Almost 55 years ago MDS Nordion and Atomic Energy of Canada developed the process for manufacturing cobalt-60 at the Chalk River Labs, in Ontario, Canada. A cobalt-59 target was introduced into a research reactor where the cobalt-59 atom absorbed one neutron to become cobalt-60. Once the cobalt-60 material was removed from the research reactor it was encapsulated in stainless steel and seal welded using a Tungsten Inert Gas weld. The first cobalt-60 sources manufactured using material from the Chalk River Labs were used in cancer

  20. 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.

  1. Electroplated zinc-cobalt alloy

    International Nuclear Information System (INIS)

    Carpenter, D.E.O.S.; Farr, J.P.G.

    2005-01-01

    Recent work on the deposition and use of ectrodeposited zinc-cobalt alloys is surveyed. Alloys containing lower of Nuclear quantities of cobalt are potentially more useful. The structures of the deposits is related to their chemical and mechanical properties. The inclusion of oxide and its role in the deposition mechanism may be significant. Chemical and engineering properties relate to the metallurgical structure of the alloys, which derives from the mechanism of deposition. The inclusion of oxides and hydroxides in the electroplate may provide evidence for this mechanism. Electrochemical impedance measurements have been made at significant deposition potentials, in alkaline electrolytes. These reveal a complex electrode behaviour which depends not only on the electrode potential but on the Co content of the electrolyte. For the relevant range of cathodic potential zinc-cobalt alloy electrodeposition occurs through a stratified interface. The formation of an absorbed layer ZnOH/sup +/ is the initial step, this inhibits the deposition of cobalt at low cathodic potentials, so explaining its 'anomalous deposition'. A porous layer of zinc forms on the adsorbed ZnOH/sup +/ at underpotential. As the potential becomes more cathodic, cobalt co- deposits from its electrolytic complex forming a metallic solid solution of Co in Zn. In electrolytes containing a high concentration of cobalt a mixed entity (ZnCo)/sub +/ is assumed to adsorb at the cathode from which a CoZn intermetallic deposits. (author)

  2. 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.

  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. 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

  5. Cobalt allergy in hard metal workers

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, T; Rystedt, I

    1983-03-01

    Hard metal contains about 10% cobalt. 853 hard metal workers were examined and patch tested with substances from their environment. Initial patch tests with 1% cobalt chloride showed 62 positive reactions. By means of secondary serial dilution tests, allergic reactions to cobalt were reproduced in 9 men and 30 women. Weak reactions could not normally be reproduced. A history of hand eczema was found in 36 of the 39 individuals with reproducible positive test reactions to cobalt, while 21 of 23 with a positive initial patch test but negative serial dilution test had never had any skin problems. Hand etching and hand grinding, mainly female activities and traumatic to the hands, were found to involve the greatest risk of cobalt sensitization. 24 individuals had an isolated cobalt allergy. They had probably been sensitized by hard metal work, while the individuals, all women, who had simultaneous nickel allergy had probably been sensitized to nickel before their employment and then became sensitized to cobalt by hard metal work. A traumatic occupation, which causes irritant contact dermatitis and/or a previous contact allergy or atopy is probably a prerequisite for the development of cobalt allergy.

  6. Fullerene–Carbene Lewis Acid–Base Adducts

    KAUST Repository

    Li, Huaping

    2011-08-17

    The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths similar to those of n-doped fullerenes were observed for the product, consistent with a net transfer of electron density to the C60 core. Corroborating information was obtained using UV photoelectron spectroscopy, which revealed that the adduct has an ionization potential ∼1.5 eV lower than that of C60. Density functional theory calculations showed that the C-C bond is polarized, with a total charge of +0.84e located on the NHC framework and -0.84e delocalized on the C 60 cage. The combination of reactivity, characterization, and theoretical studies demonstrates that fullerenes can behave as Lewis acids that react with C-based Lewis bases and that the overall process describes n-doping via C-C bond formation. © 2011 American Chemical Society.

  7. Pharmacokinetics of inorganic cobalt and a vitamin B12 supplement in the Thoroughbred horse: Differentiating cobalt abuse from supplementation.

    Science.gov (United States)

    Hillyer, L L; Ridd, Z; Fenwick, S; Hincks, P; Paine, S W

    2018-05-01

    While cobalt is an essential micronutrient for vitamin B 12 synthesis in the horse, at supraphysiological concentrations, it has been shown to enhance performance in human subjects and rats, and there is evidence that its administration in high doses to horses poses a welfare threat. Animal sport regulators currently control cobalt abuse via international race day thresholds, but this work was initiated to explore means of potentially adding to application of those thresholds since cobalt may be present in physiological concentrations. To devise a scientific basis for differentiation between presence of cobalt from bona fide supplementation and cobalt doping through the use of ratios. Six Thoroughbred horses were given 10 mL vitamin B 12 /cobalt supplement (Hemo-15 ® ; Vetoquinol, Buckingham, Buckinghamshire, UK., 1.5 mg B 12 , 7 mg cobalt gluconate = 983 μg total Co) as an i.v. bolus then an i.v. infusion (15 min) of 100 mg cobalt chloride (45.39 mg Co) 6 weeks later. Pre-and post-administration plasma and urine samples were analysed for cobalt and vitamin B 12 . Urine and plasma samples were analysed for vitamin B 12 using an immunoassay and cobalt concentrations were measured via ICP-MS. Baseline concentrations of cobalt in urine and plasma for each horse were subtracted from their cobalt concentrations post-administration for the PK analysis. Compartmental analysis was used for the determination of plasma PK parameters for cobalt using commercially available software. On administration of a vitamin B 12 /cobalt supplement, the ratio of cobalt to vitamin B 12 in plasma rapidly increased to approximately 3 and then rapidly declined below a ratio of 1 and then back to near baseline over the next week. On administration of 100 mg cobalt chloride, the ratio initially exceeded 10 in plasma and then declined with the lower 95% confidence interval remaining above a ratio of 1 for 7 days. For two horses with extended sampling, the plasma ratio remained above one for

  8. Synthesis, characterization and antimicrobial activities of novel silver(I) complexes with coumarin substituted N-heterocyclic carbene ligands.

    Science.gov (United States)

    Karataş, Mert Olgun; Olgundeniz, Begüm; Günal, Selami; Özdemir, İlknur; Alıcı, Bülent; Çetinkaya, Engin

    2016-02-15

    Eight new coumarin substituted silver(I) N-heterocyclic carbene (NHC) complexes were synthesized by the interaction of the corresponding imidazolium or benzimidazolium chlorides and Ag2O in dichloromethane at room temperature. Structures of these complexes were established on the basis of elemental analysis, (1)H NMR, (13)C NMR, IR and mass spectroscopic techniques. The antimicrobial activities of carbene precursors and silver NHC complexes were tested against standard strains: Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and the fungi Candida albicans and Candida tropicalis. Results showed that all the compounds inhibited the growth of the all bacteria and fungi strains and some complexes performed good activities against different microorganisms. Among all the compounds, the most lipophilic complex bis[1-(4-methylene-6,8-dimethyl-2H-chromen-2-one)-3-(naphthalene-2-ylmethyl)benzimidazol-2-ylidene]silver(I) dichloro argentate (5e) was found out as the most active one. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. COBALT SALTS PRODUCTION BY USING SOLVENT EXTRACTION

    Directory of Open Access Journals (Sweden)

    Liudmila V. Dyakova

    2010-06-01

    Full Text Available The paper deals with the extracting cobalt salts by using mixtures on the basis of tertiary amine from multicomponent solutions from the process of hydrochloride leaching of cobalt concentrate. The optimal composition for the extraction mixture, the relationship between the cobalt distribution coefficients and modifier’s nature and concentration, and the saltingout agent type have been determined. A hydrochloride extraction technology of cobalt concentrate yielding a purified concentrated cobalt solution for the production of pure cobalt salts has been developed and introduced at Severonikel combine.

  10. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    International Nuclear Information System (INIS)

    Qi, B.; Andrew, J. S.; Arnold, D. P.

    2017-01-01

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe_6_6Co_3_4) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe_2O_4) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  11. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    Energy Technology Data Exchange (ETDEWEB)

    Qi, B. [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States); Andrew, J. S. [University of Florida, Department of Materials Science and Engineering (United States); Arnold, D. P., E-mail: darnold@ufl.edu [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States)

    2017-03-15

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe{sub 66}Co{sub 34}) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  12. The role of friction in the mechanism of retaining the partial removable dentures with double crown system.

    Science.gov (United States)

    Dąbrowa, Tomasz; Dobrowolska, Anna; Wieleba, Wojciech

    2013-01-01

    Cylindrical telescopic crowns belong to bolt dentures, because their adhesion strength is based on the friction force. The magnitude of static and slide friction forces depends on the strain within the contact area and properties of materials employed. Friction force value between telescope elements declines in the first phase of wearing period and, subsequently, maintains particular constant value of 8 to 10 N. In the telescopic technique, homo and heterogenic joints are used. The following prosthodontic materials have been examined: goldbase alloys (Degudent Kiss, Degulor M), cobalt-base alloy (Brealloy 270), ceramics (Zircon Oxide, Zirconia) during tribological investigations on FGP composite resin. The cooperating surfaces were moistened with synthetic saliva. The research confirmed the dependence of the static friction coefficient on the contact pressure for the analyzed pairs of materials used in prosthodontics. The biggest effect of the contact pressure on the coefficient of friction value occurs when the ceramic rubs on FGP composite resin. The most stable friction coefficient in the context of contact pressure changes as well as life has been found in the case of the cobalt alloy Brealloy 270. An interesting material is a gold alloy Degulor M, for which the coefficient of friction varies only slightly with pressure in the range of 0.6 to 0.9 MPa.

  13. Preformed crowns for decayed primary molar teeth.

    Science.gov (United States)

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

    2015-12-31

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

  14. Nickel acts as an adjuvant during cobalt sensitization

    DEFF Research Database (Denmark)

    Bonefeld, Charlotte Menne; Nielsen, Morten Milek; Vennegaard, Marie T.

    2015-01-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We...... investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found...... that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses...

  15. COMPARSION EFFECTIVENES METHODS REPEIR CROWN TEETH IN DOGS

    OpenAIRE

    CHOOHNO V.S.

    2008-01-01

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

  16. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    KAUST Repository

    El-Batta, Amer

    2011-07-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis-ligated organometallic fragments with a distorted octahedral geometry. These complexes are rare examples of group IV transition-metal NHC adducts. Preliminary catalytic tests demonstrate that in the presence of methylaluminoxane (MAO) these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. © 2011 Elsevier B.V. All rights reserved.

  17. Magnetic properties of 1 : 4 complexes of CoCl2 and pyridines carrying carbenes (S(0) = 4/2, 6/2, and 8/2) in diluted frozen solution; influence of carbene multiplicity on heterospin single-molecule magnets.

    Science.gov (United States)

    Karasawa, Satoru; Nakano, Kimihiro; Tanokashira, Jun-ichi; Yamamoto, Noriko; Yoshizaki, Takahito; Koga, Noboru

    2012-11-28

    The microcrystalline sample of a parent complex, [CoCl(2)(py)(4)], showed a single-molecule magnet (SMM) behavior with an effective activation barrier, U(eff)/k(B), of 16 K for reversal of the magnetism in the presence of a dc field of 3 kOe. Pyridine ligands having 2-4 diazo moieties, DYpy; Y = 2, 3l, 3b, and 4, were prepared and confirmed to be quintet, septet, septet, and nonet in the ground state, respectively, after irradiation. The 1 : 4 complexes, CoCl(2)(DYpy)(4); Y = 2, 3l, 3b, and 4 in frozen solutions after irradiation showed the magnetic behaviors of SMMs with total spin multiplicity, S(total) = 17/2, 25/2, 25/2, and 33/2, respectively. Hysteresis loops depending on the temperature were observed and the values of coercive force, H(c), at 1.9 K were 12, 8.4, 11, and 8.1 kOe for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively. In dynamic magnetic susceptibility experiments, ac magnetic susceptibility data obeyed the Arrhenius law to give U(eff)/k(B) values of 94, 92, 93, and 87 K for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively, while the relaxation times for CoCl(2)(CYpy)(4); Y = 2 and 3l, obtained by dc magnetization decay in the range of 3.5-1.9 K slightly deviated downward from Arrhenius plots on cooling. The dynamic magnetic behaviors for CoCl(2)(CYpy)(4) including [CoCl(2)(py)(4)] and CoCl(2)(C1py)(4) suggested that the generated carbenes interacted with the cobalt ion to increase the relaxation time, τ(q), due to the spin quantum tunneling magnetization, which became larger with increasing S(total) of the complex.

  18. Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

    Directory of Open Access Journals (Sweden)

    Cristina Tubaro

    2013-02-01

    Full Text Available Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3. Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

  19. Activity relationships for aromatic crown ethers

    International Nuclear Information System (INIS)

    Wilson, Mark James

    1998-01-01

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

  20. Cobalt-60 production in CANDU reactors

    International Nuclear Information System (INIS)

    Ross, Michel; Lemire, Christian

    2002-01-01

    CANDU reactors can produce cobalt-60 very efficiently and with an interesting return on investment. This paper discusses what is needed to convert a CANDU reactor into a cobalt-60 producer: what are the different phases, the safety studies required, the physical modifications needed, and what is the minimum involvement of the utility owning the plant. The past ten years of experience of Hydro-Quebec as a cobalt-60 producer will be reviewed, including the management of the risk of both incident and electricity generation loss, and including the benefits for the utility and its personnel. Originally a simple metal used for centuries as a pigment, cobalt-59 today is transformed into cobalt-60, a radioactive element of unprecedented value. Well known in medicine for cancer treatment, cobalt-60 is also used to sterilize a wide range of disposable medical products used in hospitals and to sanitize pharmaceutical and cosmetic products. Cobalt-60 is proving to be a new and effective solution, in the food sector, for preserving harvests and controlling food-borne diseases, or to advantageously replace certain gases and chemical products which are suspected of being harmful or carcinogenic. There are also other applications, such as: hardening of some plastics, treatment of sewage sludge and elimination of harmful insect populations. With a half-life of 5,3 years, cobalt-60 is a metal not found in nature. It is a radioactive isotope produced by exposing stable nuclei of cobalt-59 to neutrons. One of the best places to find such an important neutron source is a nuclear reactor. High energy gamma rays are then emitted during the process of radioactive decay, where cobalt-60 seeks again its stable state

  1. 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.

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

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi

    2013-01-01

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

  3. 1,2,4-Triazole-based N-heterocyclic carbene complexes of gold(I): synthesis, characterization and biological activity

    Czech Academy of Sciences Publication Activity Database

    Turek, J.; Růžičková, Z.; Tloušťová, Eva; Mertlíková-Kaiserová, Helena; Günterová, Jana; Rulíšek, Lubomír; Růžička, A.

    2016-01-01

    Roč. 30, č. 5 (2016), s. 318-322 ISSN 0268-2605 R&D Projects: GA ČR(CZ) GA14-31419S; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : gold(I) complexes * N-heterocyclic carbenes * cytotoxicity * apoptosis Subject RIV: CC - Organic Chemistry Impact factor: 2.319, year: 2016

  4. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

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

    Science.gov (United States)

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

    2016-11-08

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

  6. Cobalt sensitization and dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob P

    2012-01-01

    : This clinical review article presents clinical and scientific data on cobalt sensitization and dermatitis. It is concluded that cobalt despite being a strong sensitizer and a prevalent contact allergen to come up on patch testing should be regarded as a very complex metal to test with. Exposure...

  7. Cobalt 60 availability for radiation processing

    International Nuclear Information System (INIS)

    Fraser, F.M.

    1986-01-01

    In the last 20 years, the steady and significant growth in the application of radiation processing to industrial sterilization has been seen. The principal application of this technology is the sterilization of disposable medical products, food irradiation, the irradiation of personal care goods and so on. At present, more than 70 million curies of cobalt-60 supplied by Atomic Energy of Canada Ltd. have been used for gamma processing in these applications. This is estimated to be more than 80 % of the total cobalt-60 in service in the world. Commercial food irradiation has an exciting future, and as to the impact of food irradiation on the availability of cobalt-60 over the next ten years, two principal factors must be examined, namely, the anticipated demand for cobalt-60 in all radiation processing applications, and the supply of cobalt-60 to reliably meet the expected demand. As for the cobalt-60 in service today, 90 % is used for the sterilization of disposable medical products, 5 % for food irradiation, and 5 % for other application. The demand for up to 30 million curies of cobalt-60 is expected over the next 10 years. Today, it is estimated that over 150,000 tons of spices, fruit and fish are irradiated. The potential cobalt-60 production could exceed 110 million curies per year. Gamma processing application will demand nearly 50 million curies in 1990. (Kako, I.)

  8. Synthesis of naphthalenes through three-component coupling of alkynes, Fischer carbene complexes, and benzaldehyde hydrazones via isoindole intermediates.

    Science.gov (United States)

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K; Herndon, James W

    2008-04-17

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels-Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes.

  9. Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates

    OpenAIRE

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K.; Herndon, James W.

    2008-01-01

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels–Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes.

  10. N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

    KAUST Repository

    Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

    2015-01-01

    © Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

  11. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone

    2015-03-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  12. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone; Urbina Blanco, Cé sar A.; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2015-01-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  13. One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

    Directory of Open Access Journals (Sweden)

    Priyabrata Roy

    2010-05-01

    Full Text Available One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with Fischer carbene complexes and dienophiles leading to the synthesis of quinoxaline and phenazine ring systems has been investigated. This involves the generation of furo[3,4-b]pyrazine and furo[3,4-b]quinoxaline as transient intermediates, which were trapped with Diels–Alder dienophiles. This is the first report on furo[3,4-b]pyrazine intermediates.

  14. Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates

    Science.gov (United States)

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K.; Herndon, James W.

    2008-01-01

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels–Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes. PMID:18351767

  15. Synthesis and reactions of cyclovalence isomers of azo-keto-carbenes

    International Nuclear Information System (INIS)

    Rettenbacher, A.S.

    2001-09-01

    Novel types of cycloaddition products with an azomethine imine functionality have been prepared from ω-azo-α'-diazo ketones with a carbon chain of variable length between the azo- and the keto-group; the reaction is induced by catalytical amounts of rhodium(II) acetate and occurs with the concomitant extrusion of dinitrogen. The synthesis of these cyclic azomethine imines succeeded in the course of the intramolecular reaction of the azo nitrogen atoms with a carbene/carbenoid carbon atom, in situ generated from the α-diazoketone functionality; this is a novel cyclization reaction. Some of the resulting cyclization products are stable and have been isolated, others could only be trapped with dipolarophiles as [3+2] cycloadducts. The ring-size of the heterocyclic products depends on the one hand on the length of the carbon-chain (for n = 0, 1, 2) between the carbonyl carbon atom and the quaternary aliphatic or aromatic carbon atom that blocks the tautomerization of the azo-group in the starting material. On the other hand, the ring size depends on which of the two nitrogen atoms of the azo-group undergoes the ring closure with the carbene/carbenoid carbon atom generated from the α-diazoketon functionality in the course of the reaction. By far the most serious problem in the preparation of the cyclic azomethine imines is the synthesis of the required ω-azo-α'-diazo ketones. A so far unknown property of the azo-group is its intramolecularly directed nucleophilicity toward ketenes, which emerge from acid chlorides and anhydrides, or from α-diazo ketones in the course of the Wolff rearrangement. This complicated the approach to the required ω-azo-α'-diazo ketones via these functionalities as precursors and with the desired chain length between the azo- and diazo-keto-groups. Nevertheless, these problems could be overcome by using alternative strategies. Utilizing ω-azo-α'-diazo ketones a largely commonly applicable approach to endocyclic and N

  16. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    Science.gov (United States)

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  17. Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

    KAUST Repository

    Goh, Li Min Serena; Hogerl, Manuel Peter; Jokic̈, Nadežda B.; Tanase, Alexandrina D.; Bechlars, Bettina; Baratta, Walter; Mí nk, Já nos; Kü hn, Fritz

    2014-01-01

    A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

    KAUST Repository

    Goh, Li Min Serena

    2014-01-29

    A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Synthesis of new cobalt aluminophosphate framework by opening a cobalt methylphosphonate layered material

    Czech Academy of Sciences Publication Activity Database

    Zaarour, M.; Pérez, O.; Boullay, P.; Martens, J.; Mihailova, B.; Karaghiosoff, K.; Palatinus, Lukáš; Mintova, S.

    2017-01-01

    Roč. 19, č. 34 (2017), s. 5100-5105 ISSN 1466-8033 Institutional support: RVO:68378271 Keywords : cobalt aluminophosphate * cobalt methylphosphonate * layered materials * crystallic structure * X-ray diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.474, year: 2016

  20. Radio cobalt in French rivers

    International Nuclear Information System (INIS)

    Lambrechts, A.; Baudin-Jaulent, Y.

    1996-01-01

    The isotopes 58 and 60 of cobalt present in liquid wastes from nuclear plants or from fuel reprocessing plant of Marcoule are fixed in the different compartments of French rivers. The activity levels of radio-cobalt vary according to the sampled compartments nature (bryophyta > immersed plants > sediment > fish). Elsewhere, laboratory experimentations show that the contamination of fish occurs essentially from the water way rather than from food. Cobalt is mainly fixed by kidneys; muscles is no more than 30 % of the total fish activity. (author)

  1. Molecular mechanics calculations on cobalt phthalocyanine dimers

    NARCIS (Netherlands)

    Heuts, J.P.A.; Schipper, E.T.W.M.; Piet, P.; German, A.L.

    1995-01-01

    In order to obtain insight into the structure of cobalt phthalocyanine dimers, molecular mechanics calculations were performed on dimeric cobalt phthalocyanine species. Molecular mechanics calculations are first presented on monomeric cobalt(II) phthalocyanine. Using the Tripos force field for the

  2. AN ELECTROPLATING METHOD OF FORMING PLATINGS OF NICKEL, COBALT, NICKEL ALLOYS OR COBALT ALLOYS

    DEFF Research Database (Denmark)

    1997-01-01

    An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys with reduced stresses in an electrodepositing bath of the type: Watt's bath, chloride bath or a combination thereof, by employing pulse plating with periodic reverse pulse and a sulfonated naphthalene...

  3. Reversible alkyne insertion in the benzannulation reaction of Fischer carbene complexes with alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Waters, M.L.; Bos, M.E.; Wulff, W.D. [Univ. of Chicago, IL (United States)

    1995-12-31

    The benzannulation reaction of Fischer carbene complexes with alkynes to give phenols is highly regioselective with terminal alkynes, and reasonably regioselective with internal alkynes. This has been attributed to steric factors in intermediates, where one form is favored due to close contact between the R substituent and a cis-CO ligand. Whether alkyne insertion is kinetically or thermodynamically controlled has not been determined. The authors now have evidence from regioselectivity studies that alkyne insertion into the metal-carbon bond is reversible. Implications of these results and further mechanistic considerations will be presented.

  4. 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

  5. Synthesis and anticancer activity of silver(I)-N-heterocyclic carbene complexes derived from the natural xanthine products caffeine, theophylline and theobromine.

    Science.gov (United States)

    Mohamed, Heba A; Lake, Benjamin R M; Laing, Thomas; Phillips, Roger M; Willans, Charlotte E

    2015-04-28

    A new library of silver(I)-N-heterocyclic carbene complexes prepared from the natural products caffeine, theophylline and theobromine is reported. The complexes have been fully characterised using a combination of NMR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction analysis. Furthermore, the hydrophobicity of the complexes has been measured. The silver(I)-N-heterocyclic carbenes have been evaluated for their antiproliferative properties against a range of cancer cell lines of different histological types, and compared to cisplatin. The data shows different profiles of response when compared to cisplatin in the same panel of cells, indicating a different mechanism of action. Furthermore, it appears that the steric effect of the ligand and the hydrophobicity of the complex both play a role in the chemosensitivity of these compounds, with greater steric bulk and greater hydrophilicity delivering higher cytotoxicity.

  6. The crown splash

    Science.gov (United States)

    Deegan, Robert; Brunet, Philippe; Eggers, Jens

    2008-11-01

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

  7. Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

    International Nuclear Information System (INIS)

    Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

    1993-01-01

    Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

  8. Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

    KAUST Repository

    Hong, Miao; Tang, Xiaoyan; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

    2016-01-01

    as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure

  9. 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...

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

    Directory of Open Access Journals (Sweden)

    Ovidiu Hâruţa

    2011-02-01

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

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

    Directory of Open Access Journals (Sweden)

    Ovidiu Hâruţa

    2011-06-01

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

  12. Phosphorus introduction mechanism in electrodeposited cobalt films

    International Nuclear Information System (INIS)

    Kravtchenko, Jean-Francois

    1973-01-01

    The cathodic reduction of hypophosphite, phosphite and phosphate ions was studied using chrono-potentiometry and voltammetry. Then cobalt was deposited at constant current from a bath containing one of these three compounds. The current, while giving an electrodeposition of cobalt, also enhances at the same time a chemical deposition of cobalt. It is shown that high coercive forces in cobalt films are much more related to this chemical deposition than to the simple fact that the films contain some phosphorus. (author) [fr

  13. Transition metal-induced activation of alkynes leading to metal carbene species: synthetic application to new {pi}-conjugated molecules

    Energy Technology Data Exchange (ETDEWEB)

    Abo, T; Ohe, K [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)], E-mail: ohe@scl.kyoto-u.ac.jp

    2008-03-15

    The in situ generation of furylcarbene complexes by means of transition metals was applied to catalytic carbene reactions, such as Wittig-type olefination and cycloisomerization reactions. In the presence of [Rh(OAc){sub 2}]{sub 2} as a catalyst and triphenylphosphine as a carbene accepter, carbonyl-ene-ynes 1a reacted with benzaldehyde to give a 2-styrylfuran derivative 3a. The reaction involving phosphine-ylide formation followed by Wittig-type olefination with aldehydes was applied to synthesis of furfurylidene-containing p-extended conjugated molecules. A Ruthenium catalyst underwent cycloisomerization of 1,2-bis(carbonylenyl)acetylene 10a,b to afford 2,2'-bifuran structures. The crystal structure of 5,5'-diphenyl-2,2'-bifuran 11b was determined by X-ray crystallography. The ORTEP drawings of 11b exhibited transoid and highly planar structure. The emission bands of the bisfuran 11b were observed at 414 and 440 nm, its quantum yield (84%) was higher than that of a similar 5,5'-diphenyl-2,2'-bithiophene.

  14. Cobalt reduction of NSSS valve hardfacings for ALARA

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Joo Hak; Lee, Sang Sub [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author).

  15. Cobalt reduction of NSSS valve hardfacings for ALARA

    International Nuclear Information System (INIS)

    Kim, Joo Hak; Lee, Sang Sub

    1994-07-01

    This report informs NSSS designer that replacement of materials is one of the major means of ALARA implementation, and describes that NSSS valves with high-cobalt hardfacing are significant contributors to post-shutdown radiation fields caused by activation of cobalt-59 to cobalt-60. Generic procedures for implementing cobalt reduction programs for valves are presented. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. The nuclear safety issues involved with changing valve hardfacing materials are discussed. The common methods used to deposit hardfacing materials are described together with an explanation of the wear measurements. Wear resistance, corrosion resistance, friction coefficient, and mechanical properties of candidate hardfacing alloys are given. World-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The use of low-cobalt or cobalt-free alloys in other nuclear plant components is described. 17 figs., 38 tabs., 18 refs. (Author)

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

    Directory of Open Access Journals (Sweden)

    Deborah Pacheco Lameira

    2015-01-01

    Full Text Available The purpose of this study was to evaluate the effect of design and surface finishing on fracture strength of yttria-tetragonal zirconia polycrystal (Y-TZP crowns in monolithic (1.5 mm thickness and bilayer (0.8 mm zirconia coping and 0.7 mm porcelain veneer configuration after artificial aging. Bovine incisors received crown preparation and Y-TZP crowns were manufactured using CAD/CAM technique, according to the following groups (n=10: Polished monolithic zirconia crowns (PM; Glazed monolithic zirconia crowns (GM; Bi-layer crowns (BL. Crowns were cemented with resin cement, submitted to artificial aging in a chewing simulator (2.5 million cycles/80 N/artificial saliva/37°C, and tested for fracture strength. Two remaining crowns referring to PM and GM groups were submitted to a chemical composition analysis to measure the level of yttrium after aging. One-way ANOVA and Tukey’s test (P=.05 indicated that monolithic zirconia crowns presented similar fracture strength (PM=3476.2 N ± 791.7; GM=3561.5 N ± 991.6, which was higher than bilayer crowns (2060.4 N ± 810.6. There was no difference in the yttrium content among the three surfaces evaluated in the monolithic crowns. Thus, monolithic zirconia crowns present higher fracture strength than bilayer veneered zirconia after artificial aging and surface finishing does not affect their fracture strength.

  17. The Role of External Inputs and Internal Cycling in Shaping the Global Ocean Cobalt Distribution: Insights From the First Cobalt Biogeochemical Model

    Science.gov (United States)

    Tagliabue, Alessandro; Hawco, Nicholas J.; Bundy, Randelle M.; Landing, William M.; Milne, Angela; Morton, Peter L.; Saito, Mak A.

    2018-04-01

    Cobalt is an important micronutrient for ocean microbes as it is present in vitamin B12 and is a co-factor in various metalloenzymes that catalyze cellular processes. Moreover, when seawater availability of cobalt is compared to biological demands, cobalt emerges as being depleted in seawater, pointing to a potentially important limiting role. To properly account for the potential biological role for cobalt, there is therefore a need to understand the processes driving the biogeochemical cycling of cobalt and, in particular, the balance between external inputs and internal cycling. To do so, we developed the first cobalt model within a state-of-the-art three-dimensional global ocean biogeochemical model. Overall, our model does a good job in reproducing measurements with a correlation coefficient of >0.7 in the surface and >0.5 at depth. We find that continental margins are the dominant source of cobalt, with a crucial role played by supply under low bottom-water oxygen conditions. The basin-scale distribution of cobalt supplied from margins is facilitated by the activity of manganese-oxidizing bacteria being suppressed under low oxygen and low temperatures, which extends the residence time of cobalt. Overall, we find a residence time of 7 and 250 years in the upper 250 m and global ocean, respectively. Importantly, we find that the dominant internal resupply process switches from regeneration and recycling of particulate cobalt to dissolution of scavenged cobalt between the upper ocean and the ocean interior. Our model highlights key regions of the ocean where biological activity may be most sensitive to cobalt availability.

  18. N-Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts To Generate α,β-Unsaturated Ketones.

    Science.gov (United States)

    Rajkiewicz, Adam A; Kalek, Marcin

    2018-04-06

    An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

  19. 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...

  20. Accumulation of cobalt by cephalopods

    International Nuclear Information System (INIS)

    Nakahara, Motokazu

    1981-01-01

    Accumulation of cobalt by cephalopod mollusca was investigated by radiotracer experiments and elemental analysis. In the radiotracer experiments, Octopus vulgaris took up cobalt-60 from seawater fairly well and the concentration of the nuclide in whole body attained about 150 times the level of seawater at 25th day at 20 0 C. Among the tissues and organs measured, branchial heart which is the specific organ of cephalopods showed the highest affinity for the nuclide. The organ accumulated about 50% of the radioactivity in whole body in spite of its little mass as 0.2% of total body weight. On the other hand, more than 90% of the radioactivity taken up from food (soft parts of Gomphina melanaegis labelled with cobalt-60 previously in an aquarium) was accumulated in liver at 3rd day after the single administration and then the radioactivity in the liver seemed to be distributed to other organs and tissues. The characteristic elution profiles of cobalt-60 was observed for each of the organs and tissues in Sephadex gel-filtration experiment. It was confirmed by the gel-filtration that most of cobalt-60 in the branchial heart was combined with the constituents of low molecular weights. The average concentration of stable cobalt in muscle of several species of cephalopods was 5.3 +- 3.0 μg/kg wet and it was almost comparable to the fish muscle. On the basis of soft parts, concentration of the nuclide closed association among bivalve, gastropod and cephalopod except squid that gave lower values than the others. (author)

  1. Cobalt-free nickel-base superalloys

    International Nuclear Information System (INIS)

    Koizumi, Yutaka; Yamazaki, Michio; Harada, Hiroshi

    1979-01-01

    Cobalt-free nickel-base cast superalloys have been developed. Cobalt is considered to be a beneficial element to strengthen the alloys but should be eliminated in alloys to be used for direct cycle helium turbine driven by helium gas from HTGR (high temp. gas reactor). The elimination of cobalt is required to avoid the formation of radioactive 60 Co from the debris or scales of the alloys. Cobalt-free alloys are also desirable from another viewpoint, i.e. recently the shortage of the element has become a serious problem in industry. Cobalt-free Mar-M200 type alloys modified by the additions of 0.15 - 0.2 wt% B and 1 - 1.5 wt% Hf were found to have a creep rupture strength superior or comparable to that of the original Mar-M200 alloy bearing cobalt. The ductility in tensile test at 800 0 C, as cast or after prolonged heating at 900 0 C (the tensile test was done without removing the surface layer affected by the heating), was also improved by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf. The morphology of grain boundaries became intricated by the additions of 0.15 - 0.2% B and 1 - 1.5% Hf, to such a degree that one can hardly distinguish grain boundaries by microscopes. The change in the grain boundary morphology was considered, as suggested previously by one of the authors (M.Y.), to be the reason for the improvements in the creep rupture strength and tensile ductility. (author)

  2. 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

  3. Cobalt-60 production in CANDU power reactors

    International Nuclear Information System (INIS)

    Malkoske, G.R.; Norton, J.L.; Slack, J.

    2002-01-01

    MDS Nordion has been supplying cobalt-60 sources to industry for industrial and medical purposes since 1946. These cobalt-60 sources are used in many market and product segments, but are primarily used to sterilize single-use medical products including; surgical kits, gloves, gowns, drapes, and cotton swabs. Other applications include sanitization of cosmetics, microbial reduction of pharmaceutical raw materials, and food irradiation. The technology for producing the cobalt-60 isotope was developed by MDS Nordion and Atomic Energy of Canada Limited (AECL) almost 55 years ago using research reactors at the AECL Chalk River Laboratories in Ontario, Canada. The first cobalt-60 source produced for medical applications was manufactured by MDS Nordion and used in cancer therapy. The benefits of cobalt-60 as applied to medical product manufacturing, were quickly realized and the demand for this radioisotope quickly grew. The same technology for producing cobalt-60 in research reactors was then designed and packaged such that it could be conveniently transferred to a utility/power reactor. In the early 1970's, in co-operation with Ontario Power Generation (formerly Ontario Hydro), bulk cobalt-60 production for industrial irradiation applications was initiated in the four Pickering A CANDU reactors. As the demand and acceptance of sterilization of medical products grew, MDS Nordion expanded its bulk supply by installing the proprietary Canadian technology for producing cobalt-60 in additional CANDU reactors. CANDU is unique among the power reactors of the world, being heavy water moderated and fuelled with natural uranium. They are also designed and supplied with stainless steel adjusters, the primary function of which is to shape the neutron flux to optimize reactor power and fuel bum-up, and to provide excess reactivity needed to overcome xenon-135 poisoning following a reduction of power. The reactor is designed to develop full power output with all of the adjuster

  4. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    Science.gov (United States)

    Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  5. Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid

    2015-09-01

    Full Text Available A silver-free methodology was developed for the synthesis of unprecedented N-heterocyclic carbene ruthenium indenylidene complexes bearing a bidentate picolinate ligand. The highly stable (SIPr(picolinateRuCl(indenylidene complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenylimidazolidin-2-ylidene demonstrated excellent latent behaviour in ring closing metathesis (RCM reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM and enyne metathesis reactions.

  6. Removal of Cobalt Ions by Precipitate Foam Flotation

    Energy Technology Data Exchange (ETDEWEB)

    Jung, In Ha; Lee, Jung Won [Korea Atomic Energy Research Institute, Taejon (Korea)

    1998-09-30

    Simulated waste liquid containing 50 ppm cobalt ion was tested by precipitate flotation using a sodium lauryl sulfate as a collector. The effects of initial cobalt ion concentration, pH, surfactant concentration, flotation time, gas flow rate and foreign ions on removal efficiency of cobalt ion were studied. Pretreatment of the waste liquid with 35% H{sub 2}O{sub 2} prior to precipitate flotation made shift of optimal flotation pH from the strong alkalinity to weak alkaline range and made a favorable flotation of cobalt ion in wide range of pH. For the result of this experiment, 99.8% removal efficiency was obtained on the conditions of initial cobalt ion concentration 50 ppm, pH 9.5, gas flow rate 70 ml/min, flotation time 30 min. The simulate ion was formed to be the most harmful ion against removal of cobalt by precipitate flotation of the species which were tested. The presence of 0.1 M of SO{sub 4}{sup 2-} ion decreased removal efficiency of cobalt to 90% while the cobalt were almost entirely removed in the absence of sulfate ion. (author). 11 refs., 8 figs.

  7. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne; Szeto, Kaï Chung; Norsic, Sé bastien; Garron, Anthony; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

    2011-01-01

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi

  8. 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...

  9. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  10. Synthesis and Antimicrobial Activity of Novel Ag-N-Hetero-cyclic Carbene Complexes

    Directory of Open Access Journals (Sweden)

    İlknur Özdemir

    2010-04-01

    Full Text Available A series of imidazolidinium ligand precursors are metallated with Ag2O to give silver(I N-heterocyclic carbene complexes. All compounds were fully characterized by elemental analyses, 1H-NMR, 13C-NMR and IR spectroscopy techniques. All compounds studied in this work were screened for their in vitro antimicrobial activities against the standard strains: Enterococcus faecalis (ATCC 29212, Staphylococcus aureus (ATCC 29213, Escherichia coli (ATCC 25922, Pseudomonas aeruginosa (ATCC 27853 and the fungi Candida albicans and Candida tropicalis. The new imidazolidin-2-ylidene silver complexes have been found to display effective antimicrobial activity against a series of bacteria and fungi.

  11. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Science.gov (United States)

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  12. Cobalt: for strength and color

    Science.gov (United States)

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  13. 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...

  14. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martínez, Juan Pablo

    2016-04-10

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

    2016-01-01

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2002-02-01

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

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  18. Effects of cobalt in nickel-base superalloys

    Science.gov (United States)

    Tien, J. K.; Jarrett, R. N.

    1983-01-01

    The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

  19. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    KAUST Repository

    Li, Shenyu

    2010-04-26

    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol- 2-ylidene, X = Br, 4a, and X = Cl, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO 2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h-1) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br- destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations. © 2010 American Chemical Society.

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

    Science.gov (United States)

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

    2010-01-01

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

  1. Fracture rates of IPS Empress all-ceramic crowns--a systematic review.

    Science.gov (United States)

    Heintze, Siegward D; Rousson, Valentin

    2010-01-01

    The aim of this study was to evaluate the clinical fracture rate of crowns fabricated with the pressable, leucite-reinforced ceramic IPS Empress, and relate the results to the type of tooth restored. The database SCOPUS was searched for clinical studies involving full-coverage crowns made of IPS Empress. To assess the fracture rate of the crowns in relation to the type of restored tooth and study, Poisson regression analysis was used. Seven clinical studies were identified involving 1,487 adhesively luted crowns (mean observation time: 4.5+/-1.7 years) and 81 crowns cemented with zinc-phosphate cement (mean observation time: 1.6+/-0.8 years). Fifty-seven of the adhesively luted crowns fractured (3.8%). The majority of fractures (62%) occurred between the third and sixth year after placement. There was no significant influence regarding the test center on fracture rate, but the restored tooth type played a significant role. The hazard rate (per year) for crowns was estimated to be 5 in every 1,000 crowns for incisors, 7 in every 1,000 crowns for premolars, 12 in every 1,000 crowns for canines, and 16 in every 1,000 crowns for molars. One molar crown in the zinc-phosphate group fractured after 1.2 years. Adhesively luted IPS Empress crowns showed a low fracture rate for incisors and premolars and a somewhat higher rate for molars and canines. The sample size of the conventionally luted crowns was too small and the observation period too short to draw meaningful conclusions.

  2. Cobalt: A vital element in the aircraft engine industry

    Science.gov (United States)

    Stephens, J. R.

    1981-01-01

    Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

  3. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    International Nuclear Information System (INIS)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin

    2016-01-01

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future

  4. Feasibility Study for Cobalt Bundle Loading to CANDU Reactor Core

    Energy Technology Data Exchange (ETDEWEB)

    Park, Donghwan; Kim, Youngae; Kim, Sungmin [KHNP Central Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    CANDU units are generally used to produce cobalt-60 at Bruce and Point Lepreau in Canada and Embalse in Argentina. China has started production of cobalt-60 using its CANDU 6 Qinshan Phase III nuclear power plant in 2009. For cobalt-60 production, the reactor’s full complement of stainless steel adjusters is replaced with neutronically equivalent cobalt-59 adjusters, which are essentially invisible to reactor operation. With its very high neutron flux and optimized fuel burn-up, the CANDU has a very high cobalt-60 production rate in a relatively short time. This makes CANDU an excellent vehicle for bulk cobalt-60 production. Several studies have been performed to produce cobalt-60 using adjuster rod at Wolsong nuclear power plant. This study proposed new concept for producing cobalt-60 and performed the feasibility study. Bundle typed cobalt loading concept is proposed and evaluated the feasibility to fuel management without physics and system design change. The requirement to load cobalt bundle to the core was considered and several channels are nominated. The production of cobalt-60 source is very depend on the flux level and burnup directly. But the neutron absorption characteristic of cobalt bundle is too high, so optimizing design study is needed in the future.

  5. [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

  6. Nickel, cobalt, and their alloys

    CERN Document Server

    2000-01-01

    This book is a comprehensive guide to the compositions, properties, processing, performance, and applications of nickel, cobalt, and their alloys. It includes all of the essential information contained in the ASM Handbook series, as well as new or updated coverage in many areas in the nickel, cobalt, and related industries.

  7. Navigating through the Crown land process

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  8. Cobalt sorption onto Savannah River Plant soils

    International Nuclear Information System (INIS)

    Hoeffner, S.L.

    1985-06-01

    A laboratory study of cobalt-60 sorption was conducted using Savannah River Plant soil and groundwater from the low-level waste burial ground. Systematic variation of soil and water composition indicates that cobalt sorption is most strongly a function of pH. Over a pH range of 2 to 9, the distribution coefficient ranged from 2 to more than 10,000 mL/g. Changes in clay content and in K + , Ca 2+ , or Mg 2+ concentrations influence cobalt sorption indirectly through the slight pH changes which result. The ions Na + , Cl - , and NO 3 - have no effect on cobalt sorption. Ferrous ion, added to groundwater to simulate the condition of water at the bottom of the waste trenches, accounts for part of the decrease in cobalt sorption observed with trench waters. 17 refs., 3 figs., 4 tabs

  9. 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

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

    African Journals Online (AJOL)

    2018-04-04

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

  11. 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.

  12. 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

  13. Coast redwood live crown and sapwood

    Science.gov (United States)

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

    2012-01-01

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

  14. Transport of cobalt-60 industrial radiation sources

    Science.gov (United States)

    Kunstadt, Peter; Gibson, Wayne

    This paper will deal with safety aspects of the handling of Cobalt-60, the most widely used industrial radio-isotope. Cobalt-60 is a man-made radioisotope of Cobalt-59, a naturally occurring non radioactive element, that is made to order for radiation therapy and a wide range of industrial processing applications including sterilization of medical disposables, food irradiation, etc.

  15. Retention Load Values of Telescopic Crowns Made of Y-TZP and CoCr with Y-TZP Secondary Crowns: Impact of Different Taper Angles

    Directory of Open Access Journals (Sweden)

    Susanne Merk

    2016-05-01

    Full Text Available This study aimed to examine and compare the retention load values (RL of different telescopic crown assemblies (Y-TZP and CoCr primary crowns with electroformed and Y-TZP secondary crowns each with three different taper angles (0°, 1° and 2°. Thirty Y-TZP primary crowns with electroformed gold copings (Z/G group and Y-TZP secondary crowns (Z/Z group and 30 CoCr primary crowns with electroformed gold copings (C/G group and Y-TZP secondary crowns (C/Z group, each with taper angles of 0°, 1° and 2°, were fabricated, respectively. With the exception of the electroformed gold copings, all specimens were Computer-Aided-Design/Computer-Aided-Manufacturing (CAD/CAM-milled, then sintered and afterwards manually adapted. In order to stabilize the gold copings, they were fixed in a tertiary structure. The secondary crowns were constructed with a hook, which ensured self-alignment with an upper chain. Afterwards, 20 pull-off test cycles were performed in a universal testing machine under artificial saliva and after weighing the secondary crowns with a 5 kg object for 20 s. Data were analyzed by one-way and two-way Analysis of Variance (ANOVA. C/Z with 1° showed higher (p = 0.009 RL than 0° and 2° tapers. C/G at 1° also showed higher (p = 0.001 RL than at tapers of 0° and 2°. Z/G and C/G at 0° showed lower RL than Z/Z and C/Z (p < 0.001. Primary crowns had no impact on the 0° group. Z/G showed lower RL as compared to C/Z within the 1° group (p = 0.007 and Z/Z in the 2° group (p = 0.006. The primary crown material had no influence on RL. Electroformed copings showed lower RL. Further investigations for 1° as well as for the long-term performance after thermomechanical aging are necessary.

  16. New atraumatic easy removal technique for permanently cemented crown

    Directory of Open Access Journals (Sweden)

    Pravinkumar G Patil

    2012-01-01

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

  17. 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....

  18. Extracting oil palm crown from WorldView-2 satellite image

    Science.gov (United States)

    Korom, A.; Phua, M.-H.; Hirata, Y.; Matsuura, T.

    2014-02-01

    Oil palm (OP) is the most commercial crop in Malaysia. Estimating the crowns is important for biomass estimation from high resolution satellite (HRS) image. This study examined extraction of individual OP crown from a WorldView-2 image using twofold algorithms, i.e., masking of Non-OP pixels and detection of individual OP crown based on the watershed segmentation of greyscale images. The study site was located in Beluran district, central Sabah, where matured OPs with the age ranging from 15 to 25 years old have been planted. We examined two compound vegetation indices of (NDVI+1)*DVI and NDII for masking non-OP crown areas. Using kappa statistics, an optimal threshold value was set with the highest accuracy at 90.6% for differentiating OP crown areas from Non-OP areas. After the watershed segmentation of OP crown areas with additional post-procedures, about 77% of individual OP crowns were successfully detected in comparison to the manual based delineation. Shape and location of each crown segment was then assessed based on a modified version of the goodness measures of Möller et al which was 0.3, indicating an acceptable CSGM (combined segmentation goodness measures) agreements between the automated and manually delineated crowns (perfect case is '1').

  19. Extracting oil palm crown from WorldView-2 satellite image

    International Nuclear Information System (INIS)

    Korom, A; Phua, M-H; Hirata, Y; Matsuura, T

    2014-01-01

    Oil palm (OP) is the most commercial crop in Malaysia. Estimating the crowns is important for biomass estimation from high resolution satellite (HRS) image. This study examined extraction of individual OP crown from a WorldView-2 image using twofold algorithms, i.e., masking of Non-OP pixels and detection of individual OP crown based on the watershed segmentation of greyscale images. The study site was located in Beluran district, central Sabah, where matured OPs with the age ranging from 15 to 25 years old have been planted. We examined two compound vegetation indices of (NDVI+1)*DVI and NDII for masking non-OP crown areas. Using kappa statistics, an optimal threshold value was set with the highest accuracy at 90.6% for differentiating OP crown areas from Non-OP areas. After the watershed segmentation of OP crown areas with additional post-procedures, about 77% of individual OP crowns were successfully detected in comparison to the manual based delineation. Shape and location of each crown segment was then assessed based on a modified version of the goodness measures of Möller et al which was 0.3, indicating an acceptable CSGM (combined segmentation goodness measures) agreements between the automated and manually delineated crowns (perfect case is '1')

  20. The physiological effect of cobalt on watermelon cultivation

    International Nuclear Information System (INIS)

    Yao Naihua; Jin Yafang; Sun Yaochen; Huang Yiming

    1993-01-01

    Cobalt has essential physiological action on both animals and plants. For the latter it can raise plant's nitrogen-fixing ability and saccharine content. Spray of cobalt mixed with other nutritive elements can improve the germinatit of seeds and the yield of fruit. For specifying the nutritive function of cobalt upon watermelon, isotope 60 Co was mixed into a complex leaf nutritive aqua and the regularity of transferring and absorbing cobalt in the watermelon's body was investigated

  1. Relaxation resistance of heat resisting alloys with cobalt

    International Nuclear Information System (INIS)

    Borzdyka, A.M.

    1977-01-01

    Relaxation resistance of refractory nickel-chromium alloys containing 5 to 14 % cobalt is under study. The tests involve the use of circular samples at 800 deg to 850 deg C. It is shown that an alloy containing 14% cobalt possesses the best relaxation resistance exceeding that of nickel-chromium alloys without any cobalt by a factor of 1.5 to 2. The relaxation resistance of an alloy with 5% cobalt can be increased by hardening at repeated loading

  2. gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

    Science.gov (United States)

    Hu, Mingyou; Ni, Chuanfa; Li, Lingchun; Han, Yongxin; Hu, Jinbo

    2015-11-18

    A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.

  3. Heating-induced inner-sphere substitution and reduction-oxidation reactions of the solid phenanthroline containing cobalt (2) and cobalt (3) complexes

    International Nuclear Information System (INIS)

    Palade, D.M.

    1996-01-01

    The results of the differential thermal and thermogravimetric analyses of solid phenanthroline-containing complexes of cobalt (2) and cobalt (3) in the atmosphere of the air have been analyzed. Mechanism of redox reactions occurring when cobalt (3) complexes are heated has been discussed. It is shown that some of gaseous products of the redox processes appear as a result of secondary reactions and not the processes of the ligands oxidation by Co 3+ . The influence of certain inner-sphere and coordinated anions (of I, inclusively) on cobalt (3) complexes behaviour during heating has been considered

  4. Control of carbon nanotube growth using cobalt nanoparticles as catalyst

    International Nuclear Information System (INIS)

    Huh, Yoon; Green, Malcolm L.H.; Kim, Young Heon; Lee, Jeong Yong; Lee, Cheol Jin

    2005-01-01

    We have controllably grown carbon nanotubes using uniformly distributed cobalt nanoparticles as catalyst. Cobalt nanoparticles with a uniform size were synthesized by chemical reaction and colloidal solutions including the cobalt nanoparticles were prepared. The cobalt nanoparticles were uniformly distributed on silicon substrates by a spin-coating method. Carbon nanotubes with a uniform diameter were synthesized on the cobalt nanoparticles by thermal chemical vapor deposition of acetylene gas. The density and vertical alignment of carbon nanotubes could be controlled by adjusting the density of cobalt (Co) nanoparticles

  5. A short-term clinical evaluation of IPS Empress 2 crowns.

    Science.gov (United States)

    Toksavul, Suna; Toman, Muhittin

    2007-01-01

    The aim of this study was to evaluate the clinical performance of all-ceramic crowns made with the IPS Empress 2 system after an observation period of 12 to 60 months. Seventy-nine IPS Empress 2 crowns were placed in 21 patients. The all-ceramic crowns were evaluated clinically, radiographically, and using clinical photographs. The evaluations took place at baseline (2 days after cementation) and at 6-month intervals for 12 to 60 months. Survival rate of the crowns was determined using Kaplan-Meier statistical analysis. Based on the US Public Health Service criteria, 95.24% of the crowns were rated satisfactory after a mean follow-up period of 58 months. Fracture was registered in only 1 crown. One endodontically treated tooth failed as a result of fracture at the cervical margin area. In this in vivo study, IPS Empress 2 crowns exhibited a satisfactory clinical performance during an observation period ranging from 12 to 60 months.

  6. A Catalyst-Enabled Diastereodivergent Aza-Diels-Alder Reaction: Complementarity of N-Heterocyclic Carbenes and Chiral Amines.

    Science.gov (United States)

    Rong, Zi-Qiang; Wang, Min; Chow, Chi Hao Eugene; Zhao, Yu

    2016-07-04

    Highly efficient and diastereodivergent aza-Diels-Alder reactions have been developed to access either diastereomeric series of benzofuran-fused δ-lactams and dihydropyridines in nearly perfect stereoselectivity (d.r. >20:1, >99 % ee for all examples). The complementarity of N-heterocyclic carbene and chiral amine as the catalyst was demonstrated for the first time, together with an excellent level of catalytic efficiency (1 mol % loading). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective.

    Science.gov (United States)

    Zhong, Rui; Lindhorst, Anja C; Groche, Florian J; Kühn, Fritz E

    2017-02-08

    Over the course of the past 15 years the success story of N-heterocyclic carbene (NHC) compounds in organic, inorganic, and organometallic chemistry has been extended to another dimension. The immobilization of NHC compounds, undergoing continuous diversification, broadens their range of applications and leads to new solutions for challenges in catalytic and synthetic chemistry. This review intends to present a synthetic toolkit for the immobilization of NHC compounds, giving the reader an overview on synthetic techniques and strategies available in the literature. By individually summarizing and assessing the synthetic steps of the immobilization process, a comprehensive picture of the strategies and methodologies for the immobilization of NHC compounds is presented. Furthermore, the characterization of supported NHC compounds is discussed in detail in order to set up necessary criteria for an in-depth analysis of the immobilized derivatives. Finally, the catalytic applications of immobilized NHC compounds are briefly reviewed to illustrate the practical use of this technique for a broad variety of reaction types.

  8. Dosing of anaerobic granular sludge bioreactors with cobalt: Impact of cobalt retention on methanogenic activity

    KAUST Repository

    Fermoso, Fernando G.

    2010-12-01

    The effect of dosing a metal limited anaerobic sludge blanket (UASB) reactor with a metal pulse on the methanogenic activity of granular sludge has thus far not been successfully modeled. The prediction of this effect is crucial in order to optimize the strategy for metal dosage and to prevent unnecessary losses of resources. This paper describes the relation between the initial immobilization of cobalt in anaerobic granular sludge cobalt dosage into the reactor and the evolution of methanogenic activity during the subsequent weeks. An operationally defined parameter (A0· B0) was found to combine the amount of cobalt immobilized instantaneously upon the pulse (B0) and the amount of cobalt immobilized within the subsequent 24. h (A0). In contrast with the individual parameters A0 and B0, the parameter A0· B0 correlated significantly with the methanogenic activity of the sludge during the subsequent 16 or 35. days. This correlation between metal retention and activity evolution is a useful tool to implement trace metal dosing strategies for biofilm-based biotechnological processes. © 2010.

  9. Cobalt(II) and Cobalt(III) Coordination Compounds.

    Science.gov (United States)

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  10. Twenty-nine-month follow-up of a paediatric zirconia dental crown.

    Science.gov (United States)

    Lopez Cazaux, Serena; Hyon, Isabelle; Prud'homme, Tony; Dajean Trutaud, Sylvie

    2017-06-14

    The aim of this paper is to present the long-term follow-up of one paediatric zirconia crown on a deciduous molar. Preformed crowns are part of the armamentarium in paediatric dentistry. In recent years, aesthetic alternatives to preformed metal crowns have been developed, first preveneered crowns and then zirconia crowns. This paper describes the restoration of a primary molar with a zirconia crown (EZ-Pedo, Loomis, California, USA) in an 8-year-old boy. In this clinical case, the protocol for the implementation and maintenance of zirconia crowns is detailed. The patient was followed up for 29 months until the natural exfoliation of his primary molar. The adaptation of the zirconia crown, the gingival health and the wear on the opposing tooth were considered. In this case, the paediatric zirconia crown allowed sustainable functional restoration while restoring a natural appearance of the tooth. © BMJ Publishing Group Ltd (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  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. Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

    Science.gov (United States)

    Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

    2017-07-18

    The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 21 CFR 872.3770 - Temporary crown and bridge resin.

    Science.gov (United States)

    2010-04-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

  15. Cobalt-60 control in Ontario Hydro reactors

    International Nuclear Information System (INIS)

    Lacy, C.S.

    1988-01-01

    This paper discusses the impact of specifying reduced Cobalt-59 in the primary heat transport circuit materials of construction on the radiation fields developed around the primary circuit. An eight-fold reduction in steam generator radiation fields due to Cobalt-60 has been observed for two identical sets of reactors, one with and one without Cobalt-59 control. The comparison is between eight reactors at the Pickering Nuclear Generating Station (PNGS). Units 5 to 8 (PNGS-B) are identical to Units 1 to 4 (PNGS-A) except that PNGS-B has reduced impurity Cobalt-59 in the alloys of construction and a reduced use of stellite. The effects of chemistry control are also discussed

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

    Science.gov (United States)

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

    1998-02-01

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

  17. An elevator for cobalt-60 source

    International Nuclear Information System (INIS)

    Tang Zaimin; Liang Donghu

    1990-07-01

    The elevator used for cobalt-60 source is a key device in the irradiation industry. It plays an important role in the safety and control of irradiation operation as well as the utilization rate of radiation source. From 1983 to 1986, Beijing Institute of Nuclear Engineering undertook designing of various size irradiation projects for different uses. Since then a kind of cobalt-60 source elevator suited for the irradiator of wet-source-storage has been chosen. It is reliable in the operation and complete in the function. An automatic control circuit brings the systems of cobalt-60 source elevator into an interlock system which ensures the irradiation operation safety. Besides introducing the structural features and performance of this elevator, the conditions of safety interlocking in raising or lowering the cobalt-60 source is also discussed. The discussion is from the safety viewpoint of operating an irradiator and irradiation technology

  18. Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2.

    Science.gov (United States)

    Hausmann, David; Feldmann, Claus

    2016-06-20

    The bromine-rich zinc bromides Zn6Br12(18-crown-6)2×(Br2)5 (1), Zn4Br8(18-crown-6)2×(Br2)3 (2), and Zn6Br12(18-crown-6)2×(Br2)2 (3) are prepared by reaction of ZnBr2, 18-crown-6, and elemental bromine in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2 = bis(trifluoromethylsulfonyl)amide). Zn6Br12(18-crown-6)2×(Br2)5 (1) is formed instantaneously by the reaction. Even at room temperature, compound 1 releases bromine, which was confirmed by thermogravimetry (TG) and mass spectrometry (MS). The release of Br2 can also be directly followed by the color and density of the title compounds. With controlled conditions (2 weeks, 25 °C, absence of excess Br2) Zn6Br12(18-crown-6)2×(Br2)5 (1) slowly releases bromine with conconcurrent generation of Zn4Br8(18-crown-6)2×(Br2)3 (2) (in ionic liquid) and Zn6Br12(18-crown-6)2×(Br2)2 (3) (in inert oil). All bromine-rich zinc bromides contain voluminous uncharged (e.g., Zn3Br6(18-crown-6), Zn2Br4(18-crown-6)) or ionic (e.g., [Zn2Br3(18-crown-6)](+), [(Zn2Br6)×(Br2)2](2-)) building units with dibromine molecules between the Zn oligomers and partially interconnecting the Zn-containing building units. Due to the structural similarity, the bromine release is possible via crystal-to-crystal transformation with retention of the crystal shape.

  19. Cyclometalated Iridium(III) Carbene Phosphors for Highly Efficient Blue Organic Light-Emitting Diodes.

    Science.gov (United States)

    Chen, Zhao; Wang, Liqi; Su, Sikai; Zheng, Xingyu; Zhu, Nianyong; Ho, Cheuk-Lam; Chen, Shuming; Wong, Wai-Yeung

    2017-11-22

    Five deep blue carbene-based iridium(III) phosphors were synthesized and characterized. Interestingly, one of them can be fabricated into deep blue, sky blue and white organic light-emitting diodes (OLEDs) through changing the host materials and exciton blocking layers. These deep and sky blue devices exhibit Commission Internationale de l'Éclairage (CIE) coordinates of (0.145, 0.186) and (0.152, 0.277) with external quantum efficiency (EQE) of 15.2% and 9.6%, respectively. The EQE of the deep blue device can be further improved up to 19.0% by choosing a host with suitable energy level of its lowest unoccupied molecular orbital (LUMO).

  20. 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

  1. Synthesis of axially chiral oxazoline-carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe(2).

    Science.gov (United States)

    Wang, Feijun; Li, Shengke; Qu, Mingliang; Zhao, Mei-Xin; Liu, Lian-Jun; Shi, Min

    2012-01-01

    Axially chiral oxazoline-carbene ligands with an N-naphthyl framework were successfully prepared, and their coordination behavior with AuCl·SMe(2) was also investigated, affording the corresponding Au(I) complexes in moderate to high yields.

  2. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining a...

  3. Mechanistic switch in dual gold catalysis of diynes: C(sp(3))-H activation through bifurcation--vinylidene versus carbene pathways.

    Science.gov (United States)

    Hansmann, Max M; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2013-02-25

    The other side of the mountain: Changing the framework of diyne systems opens up new cyclization modes for dual gold catalysis. Instead of a 5-endo cyclization and gold vinylidenes a 6-endo cyclization gives rise to gold-stabilized carbenes as key intermediates for selective C-H insertions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Wind Tunnel Experiments to Study Chaparral Crown Fires.

    Science.gov (United States)

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

    2017-11-14

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

  5. Crown condition dynamics of oak in southern Sweden 1988-1999.

    Science.gov (United States)

    Drobyshev, Igor; Anderson, Stefan; Sonesson, Kerstin

    2007-11-01

    Crown defoliation of oak (Quercus robur and Q. petraea) was analysed in 808 trees during three forest condition surveys (1988, 1993, and 1999) in the southern Sweden. From 1988 to 1999 crown defoliation increased by more than 20%. Changes in crown defoliation were related to the pH in the upper 20-30 cm of the mineral soils, which was closely connected to other measures of soil fertility (cation exchange capacity, CEC and C/N ratio). Trees growing on soils with a high pH (> or =4.00, in BaCl2 filtrate), high CEC and low C/N ratio had significantly lower crown defoliation than trees growing on more acid soils (pH trees with respect to crown defoliation, indicating that decline in crown condition was not due to an age-related increase in crown transparency. Considering only trees younger than 100 years, a significant interaction was observed between changes in crown defoliation and soil pH. Trees younger than 100 years old growing on more acidic soils had a greater increase in crown transparency than trees on more basic soils between 1988 and 1999. Trees > or =100 years old had significantly higher defoliation on more acidic than on more basic soils, however defoliation dynamics of these trees over 1988-99 was not related to soil acidity. Two biotic agents (insect and fungal leaf infections) evaluated in this study did not prove to be important drivers of defoliation dynamics.

  6. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil

    2010-01-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure.......Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure....

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

    Science.gov (United States)

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

    2010-01-01

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

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

    Science.gov (United States)

    KaDonna C. Randolph; Mike T. Thompson

    2010-01-01

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

  9. The role of cobalt on the creep of Waspaloy

    Science.gov (United States)

    Jarrett, R. N.; Chin, L.; Tien, J. K.

    1984-01-01

    Cobalt was systematically replaced with nickel in Waspaloy (which normally contains 13% Co) to determine the effects of cobalt on the creep behavior of this alloy. Effects of cobalt were found to be minimal on tensile strengths and microstructure. The creep resistance and the stress rupture resistance determined in the range from 704 to 760 C (1300 to 1400 C) were found to decrease as cobalt was removed from the standard alloy at all stresses and temperatures. Roughly a ten-fold drop in rupture life and a corresponding increase in minimum creep rate were found under all test conditions. Both the apparent creep activation energy and the matrix contribution to creep resistance were found to increase with cobalt. These creep effects are attributed to cobalt lowering the stacking fault energy of the alloy matrix. The creep resistance loss due to the removal of cobalt is shown to be restored by slightly increasing the gamma' volume fraction. Results are compared to a previous study on Udimet 700, a higher strength, higher gamma' volume fraction alloy with similar phase chemistry, in which cobalt did not affect creep resistance. An explanation for this difference in behavior based on interparticle spacing and cross-slip is presented.

  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. Nickel-cobalt hydroxide nanosheets: Synthesis, morphology and electrochemical properties.

    Science.gov (United States)

    Schneiderová, Barbora; Demel, Jan; Zhigunov, Alexander; Bohuslav, Jan; Tarábková, Hana; Janda, Pavel; Lang, Kamil

    2017-08-01

    This paper reports the synthesis, characterization, and electrochemical performance of nickel-cobalt hydroxide nanosheets. The hydroxide nanosheets of approximately 0.7nm thickness were prepared by delamination of layered nickel-cobalt hydroxide lactate in water and formed transparent colloids that were stable for months. The nanosheets were deposited on highly oriented pyrolytic graphite by spin coating, and their electrochemical behavior was investigated by cyclic voltammetry in potassium hydroxide electrolyte. Our method of electrode preparation allows for studying the electrochemistry of nanosheets where the majority of the active centers can participate in the charge transfer reaction. The observed electrochemical response was ascribed to mutual compensation of the cobalt and nickel response via electron sharing between these metals in the hydroxide nanosheets, a process that differentiates the behavior of nickel-cobalt hydroxide nanosheets from single nickel hydroxide or cobalt hydroxide nanosheets or their physical mixture. The presence of cobalt in the nickel-cobalt hydroxide nanosheets apparently decreases the time of electrochemical activation of the nanosheet layer, which for the nickel hydroxide nanosheets alone requires more potential sweeps. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. 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.

  13. [Clinical application of IPS-empress 2 pressable all-ceramic crowns].

    Science.gov (United States)

    Wang, Ai-jun; He, Xiao-ming; Liu, Li-xia; Zhang, Chao-biao; Zhang, Min; Shen, Bei-yong

    2007-02-01

    To evaluate the clinical prosthetic effect of IPS-Empress 2 pressahie ceramic crowns. 198 teeth of 70 patients were restored with IPS-Empress 2 pressahie ceramic crowns. The patients were asked to return in one week and every half year. The clinical prosthetic effect was evaluated. Through follow-up of 3-38 months, the veneer porcelain crowns of 3 teeth were broken. 2 crowns fall off due to teeth fracture, gingivitis occurred in 2 teeth, pulpitis or periapical periodontitis occurred in 3 teeth. The shades of 3 crowns were darkening. The prosthetic effect of 185 teeth was satisfied. The rate of satisfaction was 93.4%. IPS-Empress 2 pressable all-ceramic crown has the advantages of aesthetic effect, good hiocompatihility and simple fabrication. But its strength is not enough for posterior teeth and it can not cover the deep color of non-vital teeth and metal materials.

  14. COBALT COMPOUNDS AS ANTIDOTES FOR HYDROCYANIC ACID.

    Science.gov (United States)

    EVANS, C L

    1964-12-01

    The antidotal potency of a cobalt salt (acetate), of dicobalt edetate, of hydroxocobalamin and of cobinamide against hydrocyanic acid was examined mainly on mice and rabbits. All the compounds were active antidotes for up to twice the LD50; under some conditions for larger doses. The most successful was cobalt acetate for rabbits (5xLD50), which was effective at a molar cyanide/cobalt (CN/Co) ratio of 5, but had as a side-effect intense purgation. Hydroxocobalamin was irregular in action, but on the whole was most effective for mice (4.5xLD50 at a molar ratio of 1), and had no apparent side effects. Dicobalt edetate, at molar ratios of up to 2, was more effective for rabbits (3xLD50) than for mice (2xLD50), but had fewer side effects than cobalt acetate. The effect of thiosulphate was to augment the efficacy of dicobalt edetate and, in mice, that of hydroxocobalamin; but, apparently, in rabbits, to reduce that of hydroxocobalamin. Cobinamide, at a molar ratio of 1, was slightly more effective than hydroxocobalamin on rabbits and also less irregular in its action. Cobalt acetate by mouth was effective against orally administered hydrocyanic acid. The oxygen uptake of the body, reduced by cyanide, is rapidly reinstated when one of the cobalt antidotes has been successfully administered.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-11-01

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

  16. 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)

  17. Ceramic molar crown reproducibility by digital workflow manufacturing: An in vitro study.

    Science.gov (United States)

    Jeong, Ii-Do; Kim, Woong-Chul; Park, Jinyoung; Kim, Chong-Myeong; Kim, Ji-Hwan

    2017-08-01

    This in vitro study aimed to analyze and compare the reproducibility of zirconia and lithium disilicate crowns manufactured by digital workflow. A typodont model with a prepped upper first molar was set in a phantom head, and a digital impression was obtained with a video intraoral scanner (CEREC Omnicam; Sirona GmbH), from which a single crown was designed and manufactured with CAD/CAM into a zirconia crown and lithium disilicate crown (n=12). Reproducibility of each crown was quantitatively retrieved by superimposing the digitized data of the crown in 3D inspection software, and differences were graphically mapped in color. Areas with large differences were analyzed with digital microscopy. Mean quadratic deviations (RMS) quantitatively obtained from each ceramic group were statistically analyzed with Student's t-test (α=.05). The RMS value of lithium disilicate crown was 29.2 (4.1) µm and 17.6 (5.5) µm on the outer and inner surfaces, respectively, whereas these values were 18.6 (2.0) µm and 20.6 (5.1) µm for the zirconia crown. Reproducibility of zirconia and lithium disilicate crowns had a statistically significant difference only on the outer surface ( P <.001). The outer surface of lithium disilicate crown showed over-contouring on the buccal surface and under-contouring on the inner occlusal surface. The outer surface of zirconia crown showed both over- and under-contouring on the buccal surface, and the inner surface showed under-contouring in the marginal areas. Restoration manufacturing by digital workflow will enhance the reproducibility of zirconia single crowns more than that of lithium disilicate single crowns.

  18. Characterization of a Porous Carbon Material Functionalized with Cobalt-Oxide/Cobalt Core-Shell Nanoparticles for Lithium Ion Battery Electrodes

    KAUST Repository

    Anjum, Dalaver H.; Rasul, Shahid; Roldan-Gutierrez, Manuel A.; Da Costa, Pedro M. F. J.

    2016-01-01

    A nanoporous carbon (C) material, functionalized with Cobalt-Oxide/Cobalt (CoO/Co) core-shell nanoparticles (NPs), was structurally and chemically characterized with transmission electron microcopy (TEM) while its electrochemical response

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

    Science.gov (United States)

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

    2012-04-01

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

  20. Cobalt mineral exploration and supply from 1995 through 2013

    Science.gov (United States)

    Wilburn, David R.

    2011-01-01

    The global mining industry has invested a large amount of capital in mineral exploration and development over the past 15 years in an effort to ensure that sufficient resources are available to meet future increases in demand for minerals. Exploration data have been used to identify specific sites where this investment has led to a significant contribution in global mineral supply of cobalt or where a significant increase in cobalt production capacity is anticipated in the next 5 years. This report provides an overview of the cobalt industry, factors affecting mineral supply, and circumstances surrounding the development, or lack thereof, of key mineral properties with the potential to affect mineral supply. Of the 48 sites with an effective production capacity of at least 1,000 metric tons per year of cobalt considered for this study, 3 producing sites underwent significant expansion during the study period, 10 exploration sites commenced production from 1995 through 2008, and 16 sites were expected to begin production by 2013 if planned development schedules are met. Cobalt supply is influenced by economic, environmental, political, and technological factors affecting exploration for and production of copper, nickel, and other metals as well as factors affecting the cobalt industry. Cobalt-rich nickel laterite deposits were discovered and developed in Australia and the South Pacific and improvements in laterite processing technology took place during the 1990s and early in the first decade of the 21st century when mining of copper-cobalt deposits in Congo (Kinshasa) was restricted because of regional conflict and lack of investment in that country's mining sector. There was also increased exploration for and greater importance placed on cobalt as a byproduct of nickel mining in Australia and Canada. The emergence of China as a major refined cobalt producer and consumer since 2007 has changed the pattern of demand for cobalt, particularly from Africa and

  1. Manganese Fischer carbene chemistry: Reactions of Cp prime (CO) sub 2 Mn double bond C(OMe/OLi)R with enynes, 1-hexyne, and acrylates

    Energy Technology Data Exchange (ETDEWEB)

    Hoye, T.R.; Rehberg, G.M. (Univ. of Minnesota, Minneapolis (United States))

    1990-12-01

    Reactions of manganese carbene complexes, both the neutral methoxy and anionic lithoxy' versions, with {alpha},{omega}-enzymes give bicyclic cyclopropanes. The anion also reacts with 1-hexyne to give butenolide and with acrylate esters to give {gamma}-keto esters.

  2. Mesiodistal Crown Dimensions of Permanent Teeth in Bangladeshi Population

    Directory of Open Access Journals (Sweden)

    Saeed Hossain Khan

    2011-09-01

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

  3. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Leah J.; Holmes, Amie L. [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Maine Center for Environmental Toxicology and Health, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Department of Applied Medical Science, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Kandpal, Sanjeev Kumar; Mason, Michael D. [Department of Chemical and Biological Engineering, University of Maine, Orono, ME (United States); Zheng, Tongzhang [Department of Environmental Health Sciences, Yale School of Public Health, New Haven, CT (United States); Wise, John Pierce, E-mail: John.Wise@usm.maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Maine Center for Environmental Toxicology and Health, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States); Department of Applied Medical Science, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300 (United States)

    2014-08-01

    Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity. - Highlights: • Particulate and soluble cobalt are cytotoxic and genotoxic to human lung cells. • Soluble cobalt induces more cytotoxicity compared to particulate cobalt. • Soluble and particulate cobalt induce similar levels of genotoxicity. • Particle-cell contact is required for particulate cobalt-induced toxicity.

  4. Making a robust carbon-cobalt(III) bond

    DEFF Research Database (Denmark)

    Larsen, Erik; Madsen, Anders Østergaard; Kofod, Pauli

    2009-01-01

    The coordination ion with a well-characterized carbon-cobalt(III) bond, the (1,4,7-triazacyclononane)(1,6-diamino-3-thia-4-hexanido)cobalt(III) dication, [Co(tacn)(C-aeaps)](2+) (aeaps, for aminoethylaminopropylsulfide), has been reacted with iodomethane, and the S-methyl thionium derivative has...... been isolated. The crystal structure of the resulting [Co(tacn)(C-aeaps-SCH(3))]Br(3) x 3 H(2)O at 122 K has been determined by X-ray diffraction techniques to verify the structure. The crystal structure determination shows that the carbon-cobalt bond length is even shorter (2.001(4) A) than in [Co......(tacn)(C-aeaps)](2+) participates in bonding to cobalt(III), having implications for the transformation between the carbon- and sulfur-bound forms of the aeaps ligand....

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

    Science.gov (United States)

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

    2016-05-01

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

  6. 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

  7. Total body irradiation with a reconditioned cobalt teletherapy unit.

    Science.gov (United States)

    Evans, Michael D C; Larouche, Renée-Xavière; Olivares, Marina; Léger, Pierre; Larkin, Joe; Freeman, Carolyn R; Podgorsak, Ervin B

    2006-01-01

    While the current trend in radiotherapy is to replace cobalt teletherapy units with more versatile and technologically advanced linear accelerators, there remain some useful applications for older cobalt units. The expansion of our radiotherapy department involved the decommissioning of an isocentric cobalt teletherapy unit and the replacement of a column-mounted 4-MV LINAC that has been used for total body irradiation (TBI). To continue offering TBI treatments, we converted the decommissioned cobalt unit into a dedicated fixed-field total body irradiator and installed it in an existing medium-energy LINAC bunker. This article describes the logistical and dosimetric aspects of bringing a reconditioned cobalt teletherapy unit into clinical service as a total body irradiator.

  8. Potential for cobalt recovery from lateritic ores in Europe

    Science.gov (United States)

    Herrington, R.

    2012-04-01

    Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

  9. Titanocene–Gold Complexes Containing N-Heterocyclic Carbene Ligands Inhibit Growth of Prostate, Renal, and Colon Cancers in Vitro

    Science.gov (United States)

    2016-01-01

    We report on the synthesis, characterization, and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = −OC(O)-p-C6H4-S−) bound to gold(I)–N-heterocyclic carbene fragments through the thiolate group: [(η5-C5H5)2TiMe(μ-mba)Au(NHC)]. The cytotoxicities of the heterometallic compounds along with those of novel monometallic gold–N-heterocyclic carbene precursors [(NHC)Au(mbaH)] have been evaluated against renal, prostate, colon, and breast cancer cell lines. The highest activity and selectivity and a synergistic effect of the resulting heterometallic species was found for the prostate and colon cancer cell lines. The colocalization of both titanium and gold metals (1:1 ratio) in PC3 prostate cancer cells was demonstrated for the selected compound 5a, indicating the robustness of the heterometallic compound in vitro. We describe here preliminary mechanistic data involving studies on the interaction of selected mono- and bimetallic compounds with plasmid (pBR322) used as a model nucleic acid and the inhibition of thioredoxin reductase in PC3 prostate cancer cells. The heterometallic compounds, which are highly apoptotic, exhibit strong antimigratory effects on the prostate cancer cell line PC3. PMID:27182101

  10. Optical effects of different colors of artificial gingiva on ceramic crowns.

    Science.gov (United States)

    Wang, Jian; Lin, Jin; Gil, Mindy; Da Silva, John D; Wright, Robert; Ishikawa-Nagai, Shigemi

    2013-08-01

    The interaction between gingival color and the shade of ceramic restorations has never been fully studied. The purpose of this study is to investigate the optical effects of altering artificial gingival color on the ceramic crown shade in the cervical area. Thirty-one all-ceramic crowns of different shades were used in this study with six different artificial gingival colors. Using a spectrophotometer (Crystaleye(®) Olympus, Japan), we measured the shade of crowns in cervical areas with each of six different artificial gingiva. The crown color measured in the presence of pink artificial gingiva (control) was compared with the crown color with five other artificial gingiva. color difference values ΔE* were calculated and compared between the control group and test groups and the correlation of the artificial gingival color with the crown color was also assessed. Significant differences were found in the mean L* and a* values of all-ceramic crowns at the cervical regions in all six gingival color groups (pcolors of artificial gingiva generated clinically detectable shade differences in the cervical region of ceramic crowns. Copyright © 2013. Published by Elsevier Ltd.

  11. Clinical Performance of Pedo Jacket Crowns in Maxillary Anterior Primary Teeth.

    Science.gov (United States)

    Castro, Aimee; Badr, Sherine B Y; El-Badrawy, Wafa; Kulkarni, Gajanan

    2016-09-15

    To assess the clinical performance of Pedo Jacket crowns for restoration of carious primary anterior teeth. A total of 129 carious primary incisors and canines of 48 children younger than 71 months of age- were restored with Pedo Jacket crowns and resin-modified glass ionomer cementation. They were assessed for: ease of use; presence of recurrent decay; wear; partial or complete loss of the crown; color stability; gingival health; and overall clinical success over a 12-month follow-up. The patient's behavior at the restorative appointment during crown placement was also assessed. An overall clinical success of 89.5 percent of the teeth in 87.3 percent of the children was seen one year later. The crowns were easy to use, even in uncooperative children. The color stability, wear, plaque accumulation, and gingival health were acceptable. Discoloration, wear, or complete loss of the crown were found in 13.1 percent, 5.4 percent, and 7.6 percent of children, respectively. Although not statistically significant, failures were associated with poor patient cooperation at the time of crown placement, poor oral hygiene, or operator error. Pedo Jacket crowns are a viable treatment alternative for carious maxillary primary anterior teeth.

  12. Temperature dependent viscosity of cobalt ferrite / ethylene glycol ferrofluids

    Science.gov (United States)

    Kharat, Prashant B.; Somvanshi, Sandeep B.; Kounsalye, Jitendra S.; Deshmukh, Suraj S.; Khirade, Pankaj P.; Jadhav, K. M.

    2018-04-01

    In the present work, cobalt ferrite / ethylene glycol ferrofluid is prepared in 0 to 1 (in the step of 0.2) volume fraction of cobalt ferrite nanoparticles synthesized by co-precipitation method. The XRD results confirmed the formation of single phase spinel structure. The Raman spectra have been deconvoluted into individual Lorentzian peaks. Cobalt ferrite has cubic spinel structure with Fd3m space group. FT-IR spectra consist of two major absorption bands, first at about 586 cm-1 (υ1) and second at about 392 cm-1 (υ2). These absorption bands confirm the formation of spinel-structured cobalt ferrite. Brookfield DV-III viscometer and programmable temperature-controlled bath was used to study the relationship between viscosity and temperature. Viscosity behavior with respect to temperature has been studied and it is revealed that the viscosity of cobalt ferrite / ethylene glycol ferrofluids increases with an increase in volume fraction of cobalt ferrite. The viscosity of the present ferrofluid was found to decrease with increase in temperature.

  13. Synthesis of cobalt boride nanoparticles using radio frequency thermal plasma

    International Nuclear Information System (INIS)

    Lapitan, Jr. Lorico DS.; Ying Ying Chen; Seesoek Choe; Watanabe, Takayuki

    2012-01-01

    Nano size cobalt boride particles were synthesized from vapor phase using a 30 kw-4 MHz radio frequency (RF) thermal plasma. Cobalt and boron powder mixtures used as precursors in different composition and feed rate were evaporated immediately in the high temperature plasma and cobalt boride nanoparticles were produced through the quenching process. The x-ray diffractometry (XRD) patterns of cobalt boride nanoparticles prepared from the feed powder ratio of 1:2 and 1:3 for Co: B showed peaks that are associated with the Co 2 B and CoB crystal phases of cobalt boride. The XRD analysis revealed that increasing the powder feed rate results in a higher mass fraction and a larger crystalline diameter of cobalt boride nanoparticles. The images obtained by field emission scanning electron microscopy (FE-SEM) revealed that cobalt boride nanoparticles have a spherical morphology. The crystallite size of the particles estimated with XRD was found to be 18-22 nm. (author)

  14. Tuning and Quantifying Steric and Electronic Effects of N-Heterocyclic Carbenes

    KAUST Repository

    Falivene, Laura

    2014-07-12

    This chapter states that the main handles for tuning steric and electronic effects are the substituents on N atoms, the nature of the C4-C5 bridge (either saturated or unsaturated), and the substituents on the C4 and C5 atoms. The initial intuition that steric properties of N-heterocyclic carbenes (NHCs) could be modulated and could impact catalytic behavior stimulated the development of steric descriptors to quantify the steric requirement of different NHCs and, possibly, to compare them with tertiary phosphines. NHCs can be classified as typically strong σ-basic/π-acid ligands, although they have been also shown to exhibit reasonable π-basic properties. This electronic modularity allows NHC ligands to adapt flexibly to different chemical environments represented by a transition metal and the other ligands. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.

  15. Study to use graded cobalt adjuster in 540 MWe PHWR

    International Nuclear Information System (INIS)

    Raj, Manish; Fernando, M.P.S.; Pradhan, A.S.; Kumar, A.N.

    2007-01-01

    Full text: There are 17 adjusters in 540 MWe PHWR, which are essentially provided for xenon override function. They also provide flux flattening being in the central region of the reactor core. The present design of adjusters consists of stainless steel tube. The adjuster rods are grouped into 8 banks for movement. Since adjusters are normally fully inserted during reactor operation, they are best suited for production of cobalt 60. The nickel-plated cobalt in the form of either slugs or pellet are used for the design of cobalt pencils. The number of pencils can be varied to optimize the reactivity load and cobalt 60 production requirement. The worth and activity of cobalt adjusters have been worked out considering different pin configuration for the adjuster assembly. To start with we have assumed all adjusters throughout its length are of the same configuration. The flux depression factors within the cobalt pencils have been considered in the estimations of the specific and total cobalt 60 activities. The option of using graded cobalt adjusters, where different pin configuration along the length is considered for better flux flattening

  16. Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

    Science.gov (United States)

    Schmitt, Hans-Christian; Flock, Marco; Welz, Eileen; Engels, Bernd; Schneider, Heidi; Radius, Udo; Fischer, Ingo

    2017-03-02

    We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu 2 Im, C 11 H 20 N 2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S 1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu 2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm -1 . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Investigations on bioaccumulation of cobalt by fish eggs

    International Nuclear Information System (INIS)

    Harms, U.; Behringer, H.; Kunze, J.

    1978-01-01

    In ionized form cobalt is taken up by fish eggs directly from the water. Accumulation takes place on the chorion where the metal ions are reversibly bound to functional groups of the protein of the envelope of the egg or of the mycosa. To a small extent there occurs a transport of metal ions into the interior of the egg. It could not be clarified within the scope of the studies performed if this process is to be attributed to diffusion. Binding of the cobalt ions to the chorion leads, within hours, to a nearly uncharged final state, an apparent equilibrium, whose position is determined by the cobalt ion concentration of the breeding medium. Foreign ions (electrolytes like Ca 2+ ) lead to reduced uptake of cobalt ions, because they compete with the latter for binding places in the egg's envelope. Complex-forming substances (cysteine) result in lower absorption rates, too, the concentration of available cobalt ions in the water being reduced. (orig.) [de

  18. 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.

  19. 4-Bromoanilinium perchlorate 18-crown-6 clathrate

    Directory of Open Access Journals (Sweden)

    Min Guo

    2010-11-01

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

  20. Ballbot-type motion of N-heterocyclic carbenes on gold surfaces

    Science.gov (United States)

    Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed; Knor, Marek; Ernst, Johannes Bruno; Richter, Christian; Gao, Hong-Jun; Timmer, Alexander; Gao, Hong-Ying; Doltsinis, Nikos L.; Glorius, Frank; Fuchs, Harald

    2017-02-01

    Recently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC-gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  2. Measurement for cobalt target activity and its axial distribution

    International Nuclear Information System (INIS)

    Li Xingyuan; Chen Zigen.

    1985-01-01

    Cobalt target activity and its axial distribution are measured in process of producing radioactive isotopes 60 Co by irradiation in HFETR. Cobalt target activity is obtained with measured data at 3.60 m and 4.60 m, relative axial distribution of cobalt target activity is obtained with one at 30 cm, and axial distribution of cobalt target activity(or specific activity) is obtained with both of data. The difference between this specific activity and measured result for 60 Co teletherapy sources in the end is less than +- 5%

  3. Crown and crown-root fractures: an evaluation of the treatment plans for management proposed by 154 specialists in restorative dentistry.

    Science.gov (United States)

    de Castro, Mara Antonio Monteiro; Poi, Wilson Roberto; de Castro, José Carlos Monteiro; Panzarini, Sônia Regina; Sonoda, Celso Koogi; Trevisan, Carolina Lunardelli; Luvizuto, Eloá Rodrigues

    2010-06-01

    Traumatic tooth injuries involve function and aesthetics and cause damage that range from minimal enamel loss to complex fractures involving the pulp tissue and even loss of the tooth crown. Technical knowledge and clinical experience are essential to establish an accurate diagnosis and provide a rational treatment. The purpose of this study was to evaluate the knowledge of Restorative Dentistry specialists about the management of crown and crown-root fractures based on treatment plans proposed by these professionals for these cases. A descriptive questionnaire was mailed to 245 Restorative Dentistry specialists with questions referring to their professional profile and the treatment plans they would propose for the management of crown and crow-root fractures resulting from dental trauma. One hundred and fifty-four questionnaires were returned properly filled. The data were subjected to descriptive statistics and the chi-square test was used to determine the frequency and the level of the significance among the variables. The analysis of data showed that in spite of having a specialist title, all interviewees had great difficulty in planning the treatments. As much as 42.8% of the participants were unable to treat all types of dental trauma. Complicated and uncomplicated crown-root fractures posed the greatest difficulties for the dentists to establish adequate treatment plans because these fractures require multidisciplinary knowledge and approach for a correct case planning and prognosis.

  4. Periodontal response to all-ceramic crowns (IPS Empress) in general practice.

    Science.gov (United States)

    Al-Wahadni, A M; Mansour, Y; Khader, Y

    2006-02-01

    The purpose of this study was to investigate the periodontal response to the presence of all-ceramic crowns (IPS Empress) in general practice patients. The convenience sample included 82 IPS Empress crowns placed in 64 patients. These crowns had been in place for an average of 16.27 (SD 9.26) months and ranged from 6.2 to 48.87 months at the time of clinical examination. Periodontal health status (as determined by dental plaque, gingival health status, periodontal pockets) was assessed around all crowned teeth and around matched contralateral teeth by one calibrated examiner. Periodontal indices utilized included the Plaque Index (PI), Gingival Index (GI) and pocket depth (PD) with calibrated probes graduated in millimetres. Plaque, gingival and PD values for crowned teeth were compared with those for control teeth using Wilcoxon signed-rank test for each clinical parameters. Chi-square was used to test the significance of the difference in their distribution between crowns and control teeth. Statistically, PI (0.35), GI (0.41) and mean PD scores (1.42) of IPS Empress crowned teeth compared less favourably with scores of the control teeth (0.27, 0.23 and 0.86 respectively). Teeth with IPS Empress crowns had poorer periodontal health and more clinically evident plaque than uncrowned teeth.

  5. Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu₂(CNC(t-Bu))₂](PF₆)₂.

    Science.gov (United States)

    Riener, Korbinian; Pöthig, Alexander; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

    2015-08-01

    In recent years, the use of copper N-heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ-1,3-bis(3-tert-butylimidazolin-2-yliden-1-yl)pyridine]-1κ(4)C(2),N:N,C(2');2κ(4)C(2),N:N,C(2')-dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N-heterocyclic carbene)pyridine, ligands. Each Cu(I) atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV-Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.

  6. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  7. Aminomethylation of enals through carbene and acid cooperative catalysis: concise access to β(2)-amino acids.

    Science.gov (United States)

    Xu, Jianfeng; Chen, Xingkuan; Wang, Ming; Zheng, Pengcheng; Song, Bao-An; Chi, Yonggui Robin

    2015-04-20

    A convergent, organocatalytic asymmetric aminomethylation of α,β-unsaturated aldehydes by N-heterocyclic carbene (NHC) and (in situ generated) Brønsted acid cooperative catalysis is disclosed. The catalytically generated conjugated acid from the base plays dual roles in promoting the formation of azolium enolate intermediate, formaldehyde-derived iminium ion (as an electrophilic reactant), and methanol (as a nucleophilic reactant). This redox-neutral strategy is suitable for the scalable synthesis of enantiomerically enriched β(2) -amino acids bearing various substituents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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

  9. Characterization and Catalytic Activity of Montmorillonite K10-Supported Cobalt Catalysts

    International Nuclear Information System (INIS)

    Gobara, H.M.; Ghattas, M.S.; Henien, S.A.

    2010-01-01

    Montmorillonite K10-supported cobalt catalysts were prepared by wet impregnation method. The samples were analyzed by XRD, TPR, FTTR and BET characterization techniques. [Three phases of cobalt species were identified namely, cobalt oxide (Co 3 O 4 ), cobalt silicate (Co 2 S 1 O 4 ) and cobalt aluminate (CoAl 2 O 4 ). These species were most probably existing within the inter lamellar spaces of the meso porous montmorillonite K10 support]. The two bands observed at 1385 and 760 cm 1 were characteristic of metal species rather than the support, being mostly of Co - O bond vibration. The hysteresis loop, pore size distribution, pore volume and BET surface area were greatly affected by cobalt loading. The catalyst containing 18 wt% cobalt was the most selective sample for ethylene production from ethanol dehydration.

  10. 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)

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

    Directory of Open Access Journals (Sweden)

    Tobias Grassl

    2012-10-01

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

  12. Evaluation of sampling strategies to estimate crown biomass

    Directory of Open Access Journals (Sweden)

    Krishna P Poudel

    2015-01-01

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

  13. Radiation induced ligand loss from cobalt complexes

    International Nuclear Information System (INIS)

    Funston, A. M.; McFadyen, W.D.; Tregloan, P.A.

    2000-01-01

    Full text: Due to the rapid nature of ligand dissociation from cobalt(II) complexes the study of the rate of ligand dissociation necessitates the use of a technique such as pulse radiolysis. This allows the rapid reduction of the corresponding cobalt(III) complex by a reducing radical, such as the aquated electron, to form the cobalt(II) complex. However, to date, no systematic study of either the mechanism of reduction or the influence of the electronic structure on the rate of ligand dissociation has been carried out. In order to understand these processes more fully the mechanism of reduction of a range of related cobalt(III) complexes by the aquated electron and the subsequent rate of ligand dissociation from the resulting cobalt(II) complexes is being investigated. It has been found that a number of processes are observed following the initial rapid reaction of the cobalt(III) complex with the aquated electron. Ultimately ligand loss is observed. Depending upon the complex, the initial processes observed may include the formation of coordinated radicals and electron transfer within the complex. For complexes containing aromatic ligands such as 2,2'-bipyridine, 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine the formation of a coordinated radical is observed as the initial reduction step. The kinetics of ligand dissociation of these complexes has been determined. The loss of monodentate ligands is fast and has been indistinguishable from the reduction processes when aromatic ligands are also present in the complex. However, for diamine chelates and diimine chelates spectra of the transient species can be resolved

  14. The cobalt-60 container scanner

    International Nuclear Information System (INIS)

    Jigang, A.; Liye, Z.; Yisi, L.; Haifeng, W.; Zhifang, W.; Liqiang, W.; Yuanshi, Z.; Xincheng, X.; Furong, L.; Baozeng, G.; Chunfa, S.

    1997-01-01

    The Institute of Nuclear Energy Technology (INET) has successfully designed and constructed a container (cargo) scanner, which uses cobalt-60 of 100-300 Ci as radiation source. The following performances of the Cobalt-60 container scanner have been achieved at INET: a) IQI (Image Quality Indicator) - 2.5% behind 100 mm of steel; b) CI (Contrast Indicator) - 0.7% behind 100 mm of steel; c) SP (Steel Penetration) - 240 mm of steel; d) Maximum Dose per Scanning - 0.02mGy; e) Throughput - twenty 40-foot containers per hour. These performances are equal or similar to those of the accelerator scanners. Besides these nice enough inspection properties, the Cobalt-60 scanner possesses many other special features which are better than accelerator scanners: a) cheap price - it will be only or two tenths of the accelerator scanner's; b) low radiation intensity - the radiation protection problem is much easier to solve and a lot of money can be saved on the radiation shielding building; c) much smaller area for installation and operation; d) simple operation and convenient maintenance; e) high reliability and stability. The Cobalt-60 container (or cargo) scanner is satisfied for boundary customs, seaports, airports and railway stations etc. Because of the nice special features said above, it is more suitable to be applied widely. Its high properties and low price will make it have much better application prospects

  15. [Finite element analysis of the maxillary central incisor with crown lengthening surgery and post-core restoration in management of crown-root fracture].

    Science.gov (United States)

    Zhen, Min; Hu, Wen-jie; Rong, Qi-guo

    2015-12-18

    To construct the finite element models of maxillary central incisor and the simulations with crown lengthening surgery and post-core restoration in management of different crown-root fracture types, to investigate the stress intensity and distributions of these models mentioned above, and to analyze the indications of crown lengthening from the point of view of mechanics. An extracted maxillary central incisor and alveolar bone plaster model were scanned by Micro-CT and dental impression scanner (3shape D700) respectively. Then the 3D finite element models of the maxillary central incisor and 9 simulations with crown lengthening surgery and post-core restoration were constructed by Mimics 10.0, Geomagic studio 9.0 and ANSYS 14.0 software. The oblique static force (100 N) was applied to the palatal surface (the junctional area of the incisal 1/3 and middle 1/3), at 45 degrees to the longitudinal axis, then the von Mises stress of dentin, periodontal ligament, alveolar bone, post and core, as well as the periodontal ligament area, were calculated. A total of 10 high-precision three-dimensional finite element models of maxillary central incisor were established. The von Mises stress of models: post>dentin>alveolar bone>core>periodontal ligament, and the von Mises stress increased linearly with the augmentation of fracture degree (besides the core). The periodontal ligament area of the crown lengthening was reduced by 12% to 33%. The von Mises stress of periodontal ligament of the B2L2c, B2L3c, B3L1c, B3L2c, B3L3c models exceeded their threshold limit value, respectively. The maxillary central incisors with the labial fracture greater than three-quarter crown length and the palatal fracture deeper than 1 mm below the alveolar crest are not the ideal indications of the crown lengthening surgery.

  16. Fatigue resistance and microleakage of CAD/CAM ceramic and composite molar crowns.

    Science.gov (United States)

    Kassem, Amr S; Atta, Osama; El-Mowafy, Omar

    2012-01-01

    The aim of this study was to determine effect of compressive cyclic loading on fatigue resistance and microleakage of monolithic CAD/CAM molar ceramic and composite crowns. Thirty-two extracted molars were prepared to receive CEREC crowns according to manufacturer's guidelines using a special paralleling device (Parallel-A-Prep). Sixteen feldspathic ceramic crowns (VITABLOCS Mark II) (VMII) and 16 resin-composite crowns (Paradigm-MZ100 blocks) (PMZ) were milled using a CEREC-3D machine. Eight crowns of each group were cemented to their respective teeth using self-etching resin cement (Panavia-F-2.0) (PAN), and eight were cemented using self-adhesive resin cement (RelyX-Unicem-Clicker) (RXU). Following storage for 1 week in water, specimens were subjected to uniaxial compressive cyclic loading in an Instron testing machine at 12 Hz for 1,000,000 cycles. Load was applied at the central fossa, and the cycle range was 60-600 N. Specimens were then subjected to microleakage testing. Data were statistically analyzed using factorial ANOVA and Post Hoc (Tukey HSD) tests. All composite crowns survived compressive cyclic loading without fracture, while three ceramic crowns from the subgroup cemented with RXU developed surface cracks at the center of occlusal surfaces, extending laterally. Microleakage scores of ceramic crowns cemented with PAN were significantly lower than those of the other three subgroups (p < 0.05). After 1,000,000 cycles of compressive cyclic loading, PMZ composite molar crowns were more fatigue-resistant than VMII ceramic crowns. Cement type had a significant effect on fatigue resistance of the ceramic crowns but not the composite ones. Microleakage scores of ceramic crowns cemented with PAN were significantly lower than those of the other subgroups (p < 0.05). © 2011 by The American College of Prosthodontists.

  17. 30 CFR 250.404 - What are the requirements for the crown block?

    Science.gov (United States)

    2010-07-01

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

  18. Highly selective cobalt-catalyzed hydrovinylation of styrene

    NARCIS (Netherlands)

    Grutters, M.M.P.; Müller, C.; Vogt, D.

    2006-01-01

    The hydrovinylation reaction is a codimerization of a 1,3-diene or vinyl arene and ethene with great potential for fine chemicals and pharmaceuticals. For the first time, enantioselective cobalt-catalyzed hydrovinylations of styrene were achieved with a cobalt-based system bearing a chiral

  19. 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 ...

  20. Cobalt Blues The Story of Leonard Grimmett, the Man Behind the First Cobalt-60 Unit in the United States

    CERN Document Server

    Almond, Peter R

    2013-01-01

    For the latter half of the 20th century, cobalt-60 units were the mainstay of radiation treatments for cancer. Cobalt Blues describes the development of the first cobalt-60 unit in the United States and the man behind it, Leonard Grimmett. Conceptually conceived before World War II, it only became possible because of the development of nuclear reactors during the war. Although Grimmett conceived of and published his ideas first, the Canadians built the first units because of the capability of their reactor to produce more suitable cobalt-60 sources. This book tells the story of how Grimmett and others came together at the time that the U S Atomic Energy Agency was pushing the use of radioactivity in medicine. Due to his sudden death, very little information about Grimmett was known until recently, when various documents have come to light, allowing the full story to be told.

  1. SYNTHESIS OF 4’-ALLYLBENZO-3N-CROWN-N ETHERS AND THEIR MASS SPECTRA COMPARED WITH BENZO-3N-CROWN-N ETHERS

    OpenAIRE

    Anwar, Chairil

    2008-01-01

    Synthesis of 4’allylbenzo-3n-crown-n ethers was carried out by reacting demethylated eugenol with α,ω-dichloro-oligoethylene glycols in 1-butanol under basic condition. The mass spectra of 4’allylbenzo-3n-crown-n and benzo-3n-crown-n were investigated by mass spectrometry using electron impact under 70 eV of electron bombardment as ionisation method. The difference between the group of compounds is only the present of allyl moiety as a side chain at the other side of benzene ring. The first g...

  2. Stress distribution difference between Lava Ultimate full crowns and IPS e.max CAD full crowns on a natural tooth and on tooth-shaped implant abutments.

    Science.gov (United States)

    Krejci, Ivo; Daher, René

    2017-04-01

    The goal of this short communication is to present finite element analysis comparison of the stress distribution between CAD/CAM full crowns made of Lava Ultimate and of IPS e.max CAD, adhesively luted to natural teeth and to implant abutments with the shape of natural teeth. Six 3D models were prepared using a 3D content-creating software, based on a micro-CT scan of a human mandibular molar. The geometry of the full crown and of the abutment was the same for all models representing Lava Ultimate full crowns (L) and IPS e.max CAD full crowns (E) on three different abutments: prepared natural tooth (n), titanium abutment (t) and zirconia abutment (z). A static load of 400 N was applied on the vestibular and lingual cusps, and fixtures were applied to the base of the models. After running the static linear analysis, the post-processing data we analyzed. The stress values at the interface between the crown and the abutment of the Lt and Lz groups were significantly higher than the stress values at the same interface of all the other models. The high stress concentration in the adhesive at the interface between the crown and the abutment of the Lava Ultimate group on implants might be one of the factors contributing to the reported debondings of crowns.

  3. Sputtering on cobalt with noble gas ions

    International Nuclear Information System (INIS)

    Sarholt-Kristensen, L.; Johansen, A.; Johnson, E.

    1983-01-01

    Single crystals of cobalt have been bombarded with 80 keV Ar + ions and with 80 keV and 200 keV Xe + ions in the [0001] direction of the hcp phase and the [111] direction of the fcc phase. The sputtering yield has been measured as function of target temperature (20 0 C-500 0 C), showing a reduction in sputtering yield for 80 keV Ar + ions and 200 keV Xe + ions, when the crystal structure changes from hcp to fcc. In contrast to this, bombardment with 80 keV Xe + ions results in an increase in sputtering yield as the phase transition is passed. Sputtering yields for [111] nickel are in agreement with the sputtering yields for fcc cobalt indicating normal behaviour of the fcc cobalt phase. The higher sputtering yield of [0001] cobalt for certain combinations of ion mass and energy may then be ascribed to disorder induced partly by martensitic phase transformation, partly by radiation damage. (orig.)

  4. Comparative in vitro evaluation of CAD/CAM vs conventional provisional crowns

    Directory of Open Access Journals (Sweden)

    Adil Othman ABDULLAH

    Full Text Available ABSTRACT Objective This study compared the marginal gap, internal fit, fracture strength, and mode of fracture of CAD/CAM provisional crowns with that of direct provisional crowns. Material and Methods An upper right first premolar phantom tooth was prepared for full ceramic crown following tooth preparation guidelines. The materials tested were: VITA CAD-Temp®, Polyetheretherketone “PEEK”, Telio CAD-Temp, and Protemp™4 (control group. The crowns were divided into four groups (n=10, Group1: VITA CAD-Temp®, Group 2: PEEK, Group 3: Telio CAD-Temp, and Group 4: Protemp™4. Each crown was investigated for marginal and internal fit, fracture strength, and mode of fracture. Statistical analysis was performed using GraphPad Prism software version 6.0. Results The average marginal gap was: VITA CAD-Temp® 60.61 (±9.99 µm, PEEK 46.75 (±8.26 µm, Telio CAD-Temp 56.10 (±5.65 µm, and Protemp™4 193.07(±35.96 µm (P0.05. Conclusions CAD/CAM fabricated provisional crowns demonstrated superior fit and better strength than direct provisional crowns.

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

    Science.gov (United States)

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

    1988-08-01

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

  6. 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

  7. Displacement of screw-retained single crowns into implants with conical internal connections.

    Science.gov (United States)

    Yilmaz, Burak; Seidt, Jeremy D; McGlumphy, Edwin A; Clelland, Nancy L

    2013-01-01

    Internal conical implant-abutment connections without platforms may lead to axial displacement of crowns during screw tightening. This displacement may affect proximal contacts, incisal edge position, or occlusion. This study aimed to measure the displacement of screw-retained single crowns into an implant in three dimensions during screw tightening by hand or via torque driver. A stereolithic acrylic resin cast was created using computed tomography data from a patient missing the maxillary right central incisor. A 4.0- × 11-mm implant was placed in the edentulous site. Five porcelain-fused-to-metal single crowns were made using "cast-to" abutments. Crowns were tried on the stereolithic model, representing the patient, and hand tightened. The spatial relationship of crowns to the model after hand tightening was determined using three-dimensional digital image correlation (3D DIC), an optical measurement technique. The crowns were then tightened using a torque driver to 20 Ncm and the relative crown positions were again recorded. Testing was repeated three times for each crown, and displacement of the crowns was compared between the hand-tightened and torqued states. Commercial image correlation software was used to analyze the data. Mean vertical and horizontal crown displacement values were calculated after torqueing. The interproximal contacts were evaluated before and after torquing using an 8-μm aluminum foil shim. There were vertical and horizontal differences in crown positions between hand tightening and torqueing. Although these were small in magnitude, detectable displacements occurred in both apical and facial directions. After hand tightening, the 8-μm shim could be dragged without tearing. However, after torque tightening, the interproximal contacts were too tight and the 8-μm shim could not be dragged without tearing. Differences between hand tightening and torque tightening should be taken into consideration during laboratory and clinical

  8. Automatic crown cover mapping to improve forest inventory

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

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

    2008-10-01

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

  10. A laboratory and field evaluation of the mobility of cobalt-60/EDTA

    International Nuclear Information System (INIS)

    Jones, T.L.; Gee, G.W.; Kirkham, R.R.; Swanson, J.L.

    1983-01-01

    We have observed a time and soil type dependence in the ability of the organic complexant EDTA to keep cobalt-60 in solution. Test results indicate that short-term adsorption tests lasting 5 days or less can be misleading. In short-term tests using cobalt-60/EDTA and soil from the Hanford site, low sorption in batch tests and high mobility in column tests were observed. During long-term batch test using cobalt-60/EDTA, the percentage of cobalt remaining in solution decreased from 90% after 7 days to less than 10% after 500 days. In laboratory and field column tests where low water flow rates allowed long contact time, virtually no cobalt movement was observed even though in the field test tritium was transported over 4 meters. Long-term batch tests using cobalt-60/EDTA and soil from Savannah River burial grounds showed that cobalt remainin in solution dropped to 30% of the total cobalt added after 5 days and to less than 1% after 15 days. Batch tests using soil from Oak Ridge burial grounds were less dramatic showing cobalt in solution decreasing from 90% after 5 days to 70% after 35 days. The cobalt-60/EDTA complex appears to be dissociating and leaving uncomplexed cobalt which is readily sorbed. The dissociation seems to be rather complete in Hanford and Savannah River soil but limited in the Oak Ridge soil. The implication to waste management is that the potential for transport of cobalt by EDTA may not be as serious at all burial sites as once thought

  11. EXAFS Determination of the Structure of Cobalt in Carbon-Supported Cobalt and Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Bouwens, S.M.A.M.; Veen, J.A.R. van; Beer, V.H.J. de; Prins, R.

    1991-01-01

    The structure of the cobalt present in carbon-supported Co and Co-Mo sulfide catalysts was studied by means of X-ray absorption spectroscopy at the Co K-edge and by X-ray photoelectron spectroscopy (XPS). Thiophene hydrodesulfurization activities were used to measure the catalytic properties of

  12. Clinical performance of IPS-Empress 2 ceramic crowns inserted by general dental practitioners.

    Science.gov (United States)

    Mansour, Yasar F; Al-Omiri, Mahmoud K; Khader, Yousef Saleh; Al-Wahadni, Ahed

    2008-05-01

    The aim of this study was to evaluate the clinical performance of IPS-Empress 2(R) all-ceramic crowns placed by general dental practitioners. Eighty-two IPS-Empress 2 crowns placed in 64 patients (27 females and 37 males) were evaluated. These crowns had been in place for 15.2 to 57.2 months (mean 25.3 months, SD=9.3). Survival analysis was conducted using the Kaplan-Meier method. Of the 82 crowns 93.9% were rated satisfactory. In terms of the integrity of the restorations, fracture was observed in three crowns and two showed a crack upon transillumination. Five crowns were rated unsatisfactory for color match; one for marginal adaptation; and none for discoloration, secondary caries, or sensitivity. IPS-Empress 2(R) is a suitable material to fabricate all-ceramic crowns; when these all-ceramic crowns were inserted by general dental practitioners, they functioned satisfactorily with low failure rates during an observation period ranging between 15.2 to 57.2 months.

  13. A spot test for detection of cobalt release - early experience and findings

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Menné, Torkil; Johansen, Jeanne D

    2010-01-01

    It is often difficult to establish clinical relevance of metal exposure in cobalt-allergic patients. Dermatologists and patients may incorrectly assume that many metallic items release cobalt at levels that may cause cobalt dermatitis. Cobalt-allergic patients may be unaware that they are exposed...

  14. 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

  15. Online recovery of radiocesium from soil, cellulose and plant samples by supercritical fluid extraction employing crown ethers and calix-crown derivatives as extractants

    International Nuclear Information System (INIS)

    Kanekar, A.S.; Pathak, P.N.; Mohapatra, P.K.

    2014-01-01

    Two crown ethers (CEs) viz. dibenzo18crown6, and dibenzo12crown7 and three calix-crown derivatives viz. (octyloxy)calix[4]arene-mono-crown-6 (CMC), calix[4]arene-bis(o-benzocrown-6) (CBC), and calix[4]arene-bis(naphthocrown-6) (CNC) were evaluated for the recovery of 137 Cs from synthetic soil, cellulose (tissue paper), and plant samples by supercritical fluid extraction (SFE) route. CEs showed poor extraction of 137 Cs from soil matrix. SFE experiments using 1 × 10 -3 M solutions of CMC, CBC and CNC in acetonitrile at 3 M HNO 3 as modifiers displayed better extraction of 137 Cs, viz. 21(±2) % (CMC), 16.5(±3) % (CBC), and 4(±1) % (CNC). It was not possible to recover 137 Cs quantitatively from soil matrix. The inefficient extraction of 137 Cs from soil matrix was attributed to its incorporation into the interstitial sites. Experiments on tissue papers using CMC showed near quantitative 137 Cs recovery. On the other hand, recovery from plant samples varied between 50(±5) % (for stems) and 75(±5) % (for leaves). (author)

  16. Incentives and opportunities for reducing the cobalt content in reactor core components

    International Nuclear Information System (INIS)

    Ocken, H.

    1985-01-01

    Cobalt in core components contributes to radiation field buildup on out-of-core surfaces. Core components containing cobalt-base alloys and cobalt as an impurity are identified. The use of cobalt-free wear-resistant alloys and construction materials with lower impurity levels of cobalt is disused. It is argued that such measures are cost effective. Lower radiation fields and disposal costs will offset higher raw material costs. Component performance will not be affected. (author)

  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 of ...... abutments and did not necessarily result in an increased crown length. The distal implant papilla heightwas obviously shorter, althoughthe mesial papilla height was similar to thatof the healthy dentition.The papilla index score was tested to be a valid index for papilla fill....

  18. Removal of Cobalt Ion by Adsorbing Colloidal Flotation

    Energy Technology Data Exchange (ETDEWEB)

    Jung, In Ha; Lee, Jung Won [Korea Atomic Energy Research Institute, Taejon (Korea)

    1998-09-30

    Simulated waste liquid containing 50 ppm cobalt ion was treated by adsorbing colloidal flotation using Fe(III) or Al(III) as flocculant and a sodium lauryl sulfate as a collector. Parameters such as pH, surfactant concentration, Fe(III) or Al(III) concentration, gas flow rate, etc., were considered. The flotation with Fe(III) showed 99.8% removal efficiency of cobalt on the conditions of initial cobalt ion concentration 50 ppm, pH 9.5, gas flow rate 70 ml/min, and flotation time 30 min. When the waste solution was treated with 35% H{sub 2}O{sub 2} prior to adsorbing colloidal flotation, the optimal pH for removing cobalt shifted to weak alkaline range and flotation could be applied in wider range of pH as compared to non-use of H{sub 2}O{sub 2}. Additional use of 20 ppm Al(III) after precipitation of 50 ppm Co(II) with 50 ppm Fe(III) made the optimal pH range for preferable flotation wider. Foreign ions such as, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, Na{sup +}, Ca{sup 2+} were adopted and their effects were observed, Of which sulfate ion was found to be detrimental to removal of cobalt ion by flotation. Coprecipitation of Co ion with Fe(III) and Al(III) resulted in better removal efficiency of cobalt ion in the presence of sulfate ion. (author). 14 refs., 13 figs.

  19. Heating analysis of cobalt adjusters in reactor core

    International Nuclear Information System (INIS)

    Mei Qiliang; Li Kang; Fu Yaru

    2011-01-01

    In order to produce 60 Co source for industry and medicine applications in CANDU-6 reactor, the stainless steel adjusters were replaced with the cobalt adjusters. The cobalt rod will generate the heat when it is irradiated by neutron and γ ray. In addition, 59 Co will be activated and become 60 Co, the ray released due to 60 Co decay will be absorbed by adjusters, and then the adjusters will also generate the heat. So the heating rate of adjusters to be changed during normal operation must be studied, which will be provided as the input data for analyzing the temperature field of cobalt adjusters and the relative heat load of moderator. MCNP code was used to simulate whole core geometric configuration in detail, including reactor fuel, control rod, adjuster, coolant and moderator, and to analyze the heating rate of the stainless steel adjusters and the cobalt adjusters. The maximum heating rate of different cobalt adjuster based on above results will be provided for the steady thermal hydraulic and accident analysis, and make sure that the reactor is safe on the thermal hydraulic. (authors)

  20. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Directory of Open Access Journals (Sweden)

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

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

    OpenAIRE

    Ovidiu Hâruţa

    2011-01-01

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

  2. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  3. 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

  4. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    International Nuclear Information System (INIS)

    Myasoedova, T.G.; Ponomareva, A.V.; Zagorets, P.A.; Filippov, E.A.

    1984-01-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lgβ depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6

  5. Determination of stability constants of K and Cs nitrate complex with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Myasoedova, T G; Ponomareva, A V; Zagorets, P A; Filippov, E A [Moskovskij Khimiko-Tekhnologicheskij Inst. (USSR)

    1984-08-01

    Total stability constants of K and Cs nitrate complexes with dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 in isopropanol aqueous solutions were determined by the method of low-frequency contact conductometry. Clearly defined K/Cs selectivity is observed for the system with dibenzo-18-crown-6. It is shown that lg..beta.. depends on permittivity of the solvent. The decrease of permittivity of isopropanol aqueous solutions results in reduction of K/Cs selectivity of DB18C6.

  6. The effect of gaseous ammonia on cobalt perrhenate

    International Nuclear Information System (INIS)

    Maslov, L.P.; Men'shikov, O.D.; Borisov, V.V.; Sorokin, S.I.; Krutovertsev, S.A.; Kharkevich, S.I.; Ivanova, O.M.

    1994-01-01

    The influence of humid air ammonia mixture on crystal pentahydrate of cobalt(2) perrhenate has been studied by the methods of PES, IR spectroscopy thermal analysis and electrophysical measurements. It is shown that with an increase in ammonia content in gaseous phase cobalt perrhenate successively transforms into diaquodiammine-, tetrammine- and μ-dioxo-bis-(tetrammine) derivatives of cobalt. Reversibility of dioxocomplex formation and a correlation between the change in electrophysical properties of crystal sample and change in ammonia content in gaseous phase are pointed out. 16 refs.; 4 figs.; 1 tab

  7. Nitrogen induced ferromagnetism in Cobalt doped BaTiO3

    Directory of Open Access Journals (Sweden)

    Chandrima Mitra

    2012-09-01

    Full Text Available The electronic structure and magnetism of Cobalt doped BaTiO3 (BaTi1−xCoxO3 is investigated. Substitutional Nitrogen on an Oxygen site is found to play an important role in inducing net magnetic moments in the system. The presence of a Nitrogen atom as nearest neighbour to a Cobalt atom is crucial in producing spin splitting of both the Nitrogen and Cobalt states thereby introducing a net local magnetic moment. The introduction of Nitrogen is further found to enhance ferromagnetic interactions between Cobalt atoms.

  8. RICHMOND CROWN - FOR RESTORATION OF BADLY MUTILATED POSTERIOR TEETH : A CASE REPORT

    Directory of Open Access Journals (Sweden)

    Yadav

    2015-07-01

    Full Text Available Restoration of badly broken endodontically treated teeth is a common problem in restorative dentistry. Such teeth often require additional support from the root canal by means of a post and core restoration. In cases where tooth structure is significantly lost full coverage restorations for posterior teeth are necessary to achieve proper tooth form and function. Badly broken teeth with minimal or no crown structure require added retention and support. The Richmond crown can be a good treatment alternative for restoration of such teeth. The Richmond crown was introduced in 1878 and incorporated a threaded tube in the canal with a screw retained crown. It was later modified to eliminate the threaded tube and was redesigned as a one piece dowel and crown. This case report shows restoration of badly mutilated posterior teeth with Richmond crown.

  9. Analysis of radioactive cobalt

    International Nuclear Information System (INIS)

    1977-01-01

    This is a manual published by Science and Technology Agency, Japan, which prescribes on the analysis method for radioactive cobalt which is a typical indexing nuclide among the radioactive nuclides released from nuclear facilities. Since the released cobalt is mainly discharged to coastal region together with waste water, this manual is written for samples of sea water, sea bottom sediments and marine organisms. Radioactive cobalt includes the nuclides of 57 co, 58 Co, 60 Co, etc., the manual deals with them as a whole as 60 Co of long half life. Though 60 Co analysis has become feasible comparatively simply due to scintillation or semi-conductor spectrometry, trace 60 Co analysis is performed quantitatively by co-precipitation or collection into alumina and scintillation spectrometry. However, specific collecting operation and γ-γ coincidence measurement have been required so far. This manual employs 60 Co collection by means of ion-exchange method and measurement with low background GM counting system, to analyze quantitatively and rapidly low level 60 Co. It is primarily established as the standard analyzing method for the survey by local autonomous bodies. It is divided into 4 chapters including introduction sea water, marine organisms, and sea bottom sediments. List of required reagents is added in appendix. (Wakatsuki, Y.)

  10. Nano cobalt oxides for photocatalytic hydrogen production

    KAUST Repository

    Mangrulkar, Priti A.

    2012-07-01

    Nano structured metal oxides including TiO 2, Co 3O 4 and Fe 3O 4 have been synthesized and evaluated for their photocatalytic activity for hydrogen generation. The photocatalytic activity of nano cobalt oxide was then compared with two other nano structured metal oxides namely TiO 2 and Fe 3O 4. The synthesized nano cobalt oxide was characterized thoroughly with respect to EDX and TEM. The yield of hydrogen was observed to be 900, 2000 and 8275 mmol h -1 g -1 of photocatalyst for TiO 2, Co 3O 4 and Fe 3O 4 respectively under visible light. It was observed that the hydrogen yield in case of nano cobalt oxide was more than twice to that of TiO 2 and the hydrogen yield of nano Fe 3O 4 was nearly four times as compared to nano Co 3O 4. The influence of various operating parameters in hydrogen generation by nano cobalt oxide was then studied in detail. Copyright © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  11. Synthesis and characterization of cobalt-manganese oxides

    International Nuclear Information System (INIS)

    Valencia, J.; Arias, N.P.; Giraldo, O.; Rosales-Rivera, A.

    2012-01-01

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn 4+ to Mn 3+ . VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  12. N-Heterocyclic Carbene Complexes in Dehalogenation Reactions

    Science.gov (United States)

    Mas-Marzá, Elena; Page, Michael J.; Whittlesey, Michael K.

    Catalytic dehalogenation represents an underdeveloped transformation in M-NHC chemistry with a small number of reports detailing the reactivity of Co, Ru, Ni and Pd catalysts. In situ generated nickel and palladium NHC complexes catalyse the hydrodechlorination of aryl chlorides. Lower coordinate Ni complexes are proposed to operate in the hydrodefluorination of mono- and poly-fluorinated substrates. The single example of Ru-NHC catalysed hydrodefluorination of fully and partially fluorinated aromatic substrates is characterised by an unusual regioselectivity. The highly regioselective dehydrohalogenation of relatively unreactive alkyl halide substrates is achieved with a cobalt NHC catalyst.

  13. Rapid crown root development confers tolerance to zinc deficiency in rice

    Directory of Open Access Journals (Sweden)

    Amrit Kaur eNanda

    2016-03-01

    Full Text Available Zinc (Zn deficiency is one of the leading nutrient disorders in rice (Oryza sativa. Many studies have identified Zn efficient rice genotypes, but causal mechanisms for Zn deficiency tolerance remain poorly understood. Here we report a detailed study of the impact of Zn deficiency on crown root development of rice genotypes, differing in their tolerance to this stress. Zn deficiency delayed crown root development and plant biomass accumulation in both Zn efficient and inefficient genotypes, with the effects being much stronger in the latter. Zn efficient genotypes had developed new crown roots as early as three days after transplanting (DAT to a Zn deficient field and that was followed by a significant increase in total biomass by 7 DAT. Zn-inefficient genotypes developed few new crown roots and did not increase biomass during the first seven days following transplanting. This correlated with Zn efficient genotypes retranslocating a higher proportion of shoot Zn to their roots, compared to Zn inefficient genotypes. These latter genotypes were furthermore not efficient in utilizing the limited Zn for root development. Histological analyses indicated no anomalies in crown tissue of Zn-efficient or inefficient genotypes that would have suggested crown root emergence was impeded. We therefore conclude that the rate of crown root initiation was differentially affected by Zn deficiency between genotypes. Rapid crown root development, following transplanting, was identified as a main causative trait for tolerance to Zn deficiency and better Zn retranslocation from shoot to root was a key attribute of Zn-efficient genotypes.

  14. Total quality management of cobalt-60 sources

    International Nuclear Information System (INIS)

    Malkoske, G.R.

    1999-01-01

    Total Quality Management of Cobalt-60 sources by a supplier requires a life cycle approach to source management. This covers various aspects, including design, manufacturing, installation, field inspection, source surveillance and return of cobalt-60 sources at the end of their useful life. The Total Quality Management approach demonstrates a strong industry commitment to the beneficial use of gamma technology for industrial irradiation applications in both developed nations and in those nations who are developing their infrastructure and techniques for the beneficial use of this technology. MDS Nordion continues to demonstrate its support and commitment to the industry by developing and implementing state-of-the-art standards for the safe use of cobalt-60 sources

  15. Solubility of cobalt in primary circuit solutions

    International Nuclear Information System (INIS)

    Lambert, I.; Joyer, F.

    1992-01-01

    The solubility of cobalt ferrite (CoFe 2 O 4 ) was measured in PWR primary circuit conditions, in the temperature range 250-350 deg C, and the results were compared with the ones obtained on magnetite and nickel ferrite. As in the former cases, it was found that, in the prevailing primary circuit conditions, the solubility of the cobalt ferrite was minimum at temperatures around 300 deg C, for cobalt as well as for iron. The equilibrium iron concentration is significantly lower than in the case of magnetite. The results are discussed in relation with the POTHY code, based only on thermodynamic laws and data, used for the prediction of the primary circuit chemistry

  16. Cobalt source calibration

    International Nuclear Information System (INIS)

    Rizvi, H.M.

    1999-01-01

    The data obtained from these tests determine the dose rate of the two cobalt sources in SRTC. Building 774-A houses one of these sources while the other resides in room C-067 of Building 773-A. The data from this experiment shows the following: (1) The dose rate of the No.2 cobalt source in Building 774-A measured 1.073 x 10 5 rad/h (June 17, 1999). The dose rate of the Shepherd Model 109 Gamma cobalt source in Building 773-A measured 9.27 x 10 5 rad/h (June 25, 1999). These rates come from placing the graduated cylinder containing the dosimeter solution in the center of the irradiation chamber. (2) Two calibration tests in the 774-A source placed the graduated cylinder with the dosimeter solution approximately 1.5 inches off center in the axial direction. This movement of the sample reduced the measured dose rate 0.92% from 1.083 x 10 5 rad/h to 1.073 x 10 5 rad/h. and (3) A similar test in the cobalt source in 773-A placed the graduated cylinder approximately 2.0 inches off center in the axial direction. This change in position reduced the measured dose rate by 10.34% from 1.036 x 10 6 to 9.27 x 10 5 . This testing used chemical dosimetry to measure the dose rate of a radioactive source. In this method, one determines the dose by the chemical change that takes place in the dosimeter. For this calibration experiment, the author used a Fricke (ferrous ammonium sulfate) dosimeter. This solution works well for dose rates to 10 7 rad/h. During irradiation of the Fricke dosimeter solution the Fe 2+ ions ionize to Fe 3+ . When this occurs, the solution acquires a slightly darker tint (not visible to the human eye). To determine the magnitude of the change in Fe ions, one places the solution in an UV-VIS Spectrophotometer. The UV-VIS Spectrophotometer measures the absorbency of the solution. Dividing the absorbency by the total time (in minutes) of exposure yields the dose rate

  17. Piezoelectric properties and thermal stabilities of cobalt-modified potassium bismuth titanate

    International Nuclear Information System (INIS)

    Guo, Zhen-Lei; Wang, Chun-Ming; Zhao, Tian-Long; Yu, Si-Long; Cao, Zhao-Peng

    2013-01-01

    The cobalt-modified potassium bismuth titanate (K 0.5 Bi 4.5 Ti 4 O 15 , KBT) piezoelectric ceramics have been prepared using conventional solid–state reaction. X-ray diffraction analysis revealed that the cobalt-modified KBT ceramics have a pure four-layer (m = 4) Aurivillius-type structure. The dielectric, ferroelectric, and piezoelectric properties of cobalt-modified KBT ceramics were investigated in detail. The piezoelectric activities of KBT ceramics were significantly improved by the cobalt modification. The reasons for piezoelectric activities enhancement with cobalt modification were given. The piezoelectric coefficient d 33 and Curie temperature T c for the 5 mol% cobalt-modified KBT ceramics (KBT-Co5) were found to be 28 pC/N and 575 °C, respectively. The DC resistivity, frequency constants (N p and N t ), and electromechanical properties at elevated temperature were investigated, indicating the cobalt-modified KBT piezoelectric ceramics possess stable piezoelectric properties up to 500 °C. The results show the cobalt-modified KBT ceramics are potential materials for high temperature piezoelectric applications. - Highlights: • We examine the piezoelectric properties of the cobalt-modified K 0.5 Bi 4.5 Ti 4 O 15 . • A high level of piezoelectric activities (d 33 = 28 pC/N) are obtained. • High Curie temperature (T c = 575 °C) is acquired for the optimal composition. • The Co-modified K 0.5 Bi 4.5 Ti 4 O 15 is promising as high temperature materials

  18. Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0(2,6)]decane.

    Science.gov (United States)

    Hudzik, Jason M; Castillo, Álvaro; Bozzelli, Joseph W

    2015-09-24

    Exo-tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is an interesting strained ring compound and the single-component high-energy density hydrocarbon fuel known as JP-10. Important initial reactions of TCD at high temperatures could cleave a strained carbon-carbon (C-C) bond in the ring system creating diradicals also constrained by the remaining ring system. This study determines the thermochemical properties of these diradicals (TCD-H2 mJ-nJ where m and n correspond to the cleaved carbons sites) including the carbon-carbon bond dissociation energy (C-C BDE) corresponding to the cleaved TCD site. Thermochemical properties including enthalpies (ΔH°f298), entropies (S(T)), heat capacities (Cp(T)), and C-H and C-C BDEs for the parent (TCD-H2 m-n), radical (TCD-H2 mJ-n and m-nJ), diradical (TCD-H2 mJ-nJ), and carbene (TCD-H2 mJJ-n and m-nJJ) species are determined. Structures, vibrational frequencies, moments of inertia, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2 m-n parent and radical species are determined using the B3LYP density functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods. For singlet and triplet TCD diradicals and carbenes, M06-2X, ωB97X-D, and CCSD(T) methods are included in the analysis to determine ΔH°f298 values. The C-C BDEs are further calculated using CASMP2(2,2)/aug-cc-pvtz//CASSCF(2,2)/cc-pvtz and with the CASMP2 energies extrapolated to the complete basis set limit. The bond energies calculated with these methods are shown to be comparable to the other calculation methods. Isodesmic work reactions are used for enthalpy analysis of these compounds for effective cancelation of systematic errors arising from ring strain. C-C BDEs range from 77.4 to 84.6 kcal mol(-1) for TCD diradical singlet species. C-H BDEs for the parent TCD-H2 m-n carbon sites range from 93 to 101 kcal mol(-1) with a

  19. CAD/CAM glass ceramics for single-tooth implant crowns: a finite element analysis.

    Science.gov (United States)

    Akça, Kvanç; Cavusoglu, Yeliz; Sagirkaya, Elcin; Aybar, Buket; Cehreli, Murat Cavit

    2013-12-01

    To evaluate the load distribution of CAD/CAM mono-ceramic crowns supported with single-tooth implants in functional area. A 3-dimensional numerical model of a soft tissue-level implant was constructed with cement-retained abutment to support glass ceramic machinable crown. Implant-abutment complex and the retained crown were embedded in a Ø 1.5 × 1.5 cm geometric matrix for evaluation of mechanical behavior of mono-ceramic CAD/CAM aluminosilicate and leucite glass crown materials. Laterally positioned axial load of 300 N was applied on the crowns. Resulting principal stresses in the mono-ceramic crowns were evaluated in relation to different glass ceramic materials. The highest compressive stresses were observed at the cervical region of the buccal aspect of the crowns and were 89.98 and 89.99 MPa, for aluminosilicate and leucite glass ceramics, respectively. The highest tensile stresses were observed at the collar of the lingual part of the crowns and were 24.54 and 25.39 MPa, respectively. Stresses induced upon 300 N static loading of CAD/CAM aluminosalicate and leucite glass ceramics are below the compressive strength of the materials. Impact loads may actuate the progress to end failure of mono-ceramic crowns supported by metallic implant abutments.

  20. Evaluation of different sterilization and disinfection methods on commercially made preformed crowns.

    Science.gov (United States)

    Yilmaz, Y; Guler, C

    2008-12-01

    The aim of this study was to evaluate the changes caused by different sterilization or disinfection methods on the vestibular surface of four commercially made preformed crowns using stereomicroscopy and scanning electron microscopy (SEM). Preformed crowns (NuSmile Primary Anterior Crown (NSC), Kinder Krowns (KK), Pedo Pearls (PP) and polycarbonate crowns (PC)) were sterilized and/or disinfected by one of the following techniques: no sterilization or disinfection (G1 control group); steam autoclaving at 134 degrees C (30 psi) for 4 min (G2); steam autoclaving at 134 degrees C (30 psi) for 12 min (G3); steam autoclaving at 121 degrees C (15 psi) for 30 min (G4); and ultrasonication in a bath containing 4% Lysetol AF for 5 min at room temperature (chemical disinfection) (G5). Scanning electron micrographs of the crowns were taken before and after their sterilization or disinfection. The changes on the vestibular surface were then scored for the presence or absence of crazing, contour alteration, fracturing, and vestibular surface changes. The data were analyzed statistically using the chi-square test. No changes were observed before and after sterilization or disinfection in the stereomicroscopic evaluation of the vestibular surface of the crowns. However, all methods in which steam autoclaving was used to sterilize the crowns caused significant (P < 0.05) crazing and contour alterations of the vestibular surface of the crowns when they were examined by SEM. Chemical disinfection using an aldehyde-free disinfectant is the preferred method of disinfection for crowns that have been used previously in other dental patients.

  1. The cobalt radioactive isotopes in environment; Les isotopes radioactifs du cobalt dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-07-01

    For the year 1993 the total activity released in cobalt is 69 GBq for the whole of nuclear power plants. The part of activity in cobalt for La Hague in 1993 is 8 GBq of {sup 58}Co and 2 GBq of {sup 60}Co. The radioactive isotopes released by nuclear power plants or the reprocessing plant of La Hague under liquid effluents are shared by half between {sup 58}Co and {sup 60}Co. The exposure to sealed sources is the most important risk for the cobalt. The risk of acute exposure can associate a local irradiation of several decades of grays inducing a radiological burns, deep burn to treat in surgery by resection or graft even amputation. A global irradiation of organism for several grays induces an acute irradiation syndrome, often serious. At long term the stochastic effects are represented by leukemia and radio-induced cancers. The increase of probability of their occurrence is 1% by sievert. We must remind that the natural spontaneous probability is 25%. (N.C.)

  2. Separation of cobalt from synthetic intermediate and decontamination radioactive wastes using polyurethane foam

    International Nuclear Information System (INIS)

    Rao, S.V.S.; Lal, K.B.; Narasimhan, S.V.; Ahmed, J.

    1997-01-01

    Studies have been carried out on the removal of radioactive cobalt ( 60 Co) from synthetic intermediate level waste (ILW) and decontamination waste using neat polyurethane (PU) foam as well as n-tributyl phosphate-polyurethane (TBP-PU) foam. The radioactive cobalt has been extracted on the PU foam as cobalt thiocyanate from the ILW. Maximum removal of cobalt has been observed when the concentration of thiocyanate in the solution is about 0.4 M. Cobalt can be separated from decontamination waste containing ethylenediaminetetraacetic acid (EDTA) and iron(II). The extent of extraction of cobalt is slow and the separation of iron and cobalt is better with the neat PU foam compared to the TBP-PU foam. The presence of iron in the decontamination waste facilitates the extraction of cobalt thiocyanate on the PU foam. Column studies have been carried out in order to extend these studies to the plant scale. The capacities of the PU foams for cobalt have been determined. The effect of density and the surface area of PU foam have been investigated. Fourier Transform Infrared (FT-IR) spectral studies have been conducted to find out the interaction between PU foam and cobalt thiocyanate species

  3. Characterization of a Cobalt-Tungsten Interconnect

    DEFF Research Database (Denmark)

    Harthøj, Anders; Holt, Tobias; Caspersen, Michael

    2012-01-01

    is to act both as a diffusion barrier for chromium and provide better protection against high temperature oxidation than a pure cobalt coating. This work presents a characterization of a cobalt-tungsten alloy coating electrodeposited on the ferritic steel Crofer 22 H which subsequently was oxidized in air......A ferritic steel interconnect for a solid oxide fuel cell must be coated in order to prevent chromium evaporation from the steel substrate. The Technical University of Denmark and Topsoe Fuel Cell have developed an interconnect coating based on a cobalt-tungsten alloy. The purpose of the coating...... for 300 h at 800 °C. The coating was characterized with Glow Discharge Optical Spectroscopy (GDOES), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The oxidation properties were evaluated by measuring weight change of coated samples of Crofer 22 H and Crofer 22 APU as a function...

  4. Association between cobalt allergy and dermatitis caused by leather articles

    DEFF Research Database (Denmark)

    Bregnbak, David; Thyssen, Jacob P; Zachariae, Claus

    2015-01-01

    BACKGROUND: Cobalt is a strong skin sensitizer and a prevalent contact allergen. Recent studies have recognized exposure to leather articles as a potential cause of cobalt allergy. OBJECTIVES: To examine the association between contact allergy to cobalt and a history of dermatitis resulting from...... exposure to leather. METHODS: A questionnaire case-control study was performed: the case group consisted of 183 dermatitis patients with a positive patch test reaction to cobalt chloride and a negative patch test reaction to potassium dichromate; the control group consisted of 621 dermatitis patients who...... did not react to either cobalt or chromium in patch testing. Comparisons were made by use of a χ(2) -test, Fisher's exact, and the Mann-Whitney test. Logistic regression analyses were used to test for associations while taking confounding factors into consideration. RESULTS: Leather was observed...

  5. 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 ...

  6. Multiwalled Carbon Nanotubes Decorated with Cobalt Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    D. G. Larrude

    2012-01-01

    Full Text Available Multiwalled carbon nanotubes (MWCNTs synthesized by spray pyrolysis were decorated with cobalt oxide nanoparticles using a simple synthesis route. This wet chemistry method yielded nanoparticles randomly anchored to the surface of the nanotubes by decomposition of cobalt nitrate hexahydrate diluted in acetone. Electron microscopy analysis indicated that dispersed particles were formed on the MWCNTs walls. The average size increased with the increasing concentration of cobalt nitrate in acetone in the precursor mixture. TEM images indicated that nanoparticles were strongly attached to the tube walls. The Raman spectroscopy results suggested that the MWCNT structure was slightly damaged after the nanoparticle growth.

  7. Transport properties of cobalt at low temperatures

    DEFF Research Database (Denmark)

    Radharkishna, P.; Nielsen, Mourits

    1965-01-01

    Measurements are made of electrical resistivity, absolute thermoelectric power, and thermal conductivity of polycrystalline cobalt between 1.2 and 6 K; results are discussed on basis of inter-electronic scattering.......Measurements are made of electrical resistivity, absolute thermoelectric power, and thermal conductivity of polycrystalline cobalt between 1.2 and 6 K; results are discussed on basis of inter-electronic scattering....

  8. Perfluorinated cobalt phthalocyanine effectively catalyzes water electrooxidation

    KAUST Repository

    Morlanes, Natalia Sanchez

    2014-12-08

    Efficient electrocatalysis of water oxidation under mild conditions at neutral pH was achieved by a fluorinated cobalt phthalocyanine immobilized on fluorine-doped tin oxide (FTO) surfaces with an onset potential at 1.7 V vs. RHE. Spectroscopic, electrochemical, and inhibition studies indicate that phthalocyanine molecular species are the operational active sites. Neither free cobalt ions nor heterogeneous cobalt oxide particles or films were observed. During long-term controlled-potential electrolysis at 2 V vs. RHE (phosphate buffer, pH 7), electrocatalytic water oxidation was sustained for at least 8 h (TON ≈ 1.0 × 105), producing about 4 μmol O2 h-1 cm-2 with a turnover frequency (TOF) of about 3.6 s-1 and no measurable catalyst degradation.

  9. A spot test for detection of cobalt release – early experience and findings

    DEFF Research Database (Denmark)

    Thyssen, Jacob P.; Menné, Torkil; Johansen, Jeanne D.

    2010-01-01

    Background: It is often difficult to establish clinical relevance of metal exposure in cobalt-allergic patients. Dermatologists and patients may incorrectly assume that many metallic items release cobalt at levels that may cause cobalt dermatitis. Cobalt-allergic patients may be unaware that they...

  10. Oxidative N-Heterocyclic Carbene-Catalyzed γ-Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds.

    Science.gov (United States)

    Zheng, Peng-Cheng; Cheng, Jiajia; Su, Shihu; Jin, Zhichao; Wang, Yu-Huang; Yang, Song; Jin, Lin-Hong; Song, Bao-An; Chi, Yonggui Robin

    2015-07-06

    The reaction mechanism of the γ-carbon addition of enal to imine under oxidative N-heterocyclic carbene catalysis is studied experimentally. The oxidation, γ-carbon deprotonation, and nucleophilic addition of γ-carbon to imine were found to be facile steps. The results of our study also provide highly enantioselective access to tricyclic sulfonyl amides that exhibit interesting antimicrobial activities against X. oryzae, a bacterium that causes bacterial disease in rice growing. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Assessment of cobalt levels in wastewater, soil and vegetable ...

    African Journals Online (AJOL)

    User

    Key words: Cobalt level, Kubanni River, soil, vegetable, wastewater. INTRODUCTION. Cobalt is ... metals released into the environment from a variety of anthropogenic activities ..... Heavy Metal Stress in Plants, 2nd Edition,. Springer,. United.

  12. Synthesis and phosphatase activity of a Cobalt(II) phenanthroline ...

    Indian Academy of Sciences (India)

    MAMONI GARAI

    2017-09-19

    Sep 19, 2017 ... Synthesis and phosphatase activity of a Cobalt(II) phenanthroline complex. MAMONI GARAIa ... tion, cobalt complexes have gained importance because of their application as ... 2.3 Physical measurements. Infrared spectrum ...

  13. Correlation between morphology and magnetic properties of electrochemically produced cobalt powder particles

    Directory of Open Access Journals (Sweden)

    Maksimović Vesna M.

    2015-01-01

    Full Text Available Cobalt 3D powder particles were successfully prepared by the galvanostatic electrodeposition. Electrodeposited cobalt powder were characterized by X-ray diffraction (XRD, scanning electron microscope (SEM, Energy Dispersive Spectroscopy (EDS analysis and SQUID magnetometry. It has been shown that morphology, structure and magnetic properties of cobalt particles are closely associated and can be easily controlled by adjusting process parameters of electrodeposition. Morphology of cobalt powder particles is strongly affected by hydrogen evolution reaction as a parallel reaction to cobalt electrodeposition. Depending on the applied current density, the two types of powder particles were formed: dendrites at lower and spongy-like particles at higher current densities. Morphologies and structures of powder particles are correlated with their magnetic properties, and compared with those of the bulk cobalt. In comparison with the properties of bulk cobalt, the obtained 3D structures exhibited a decreased saturation magnetization (MS, but an enhanced coercivity (HC which is explained by their peculiar morphology. [Projekat Ministarstva nauke Republike Srbije, br. III 45012

  14. 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.

  15. 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.

  16. Synthesis and characterization of cobalt-manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Valencia, J. [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis 55455-0153 (United States); Arias, N.P. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Departamento de Ingenieria Electrica, Electronica y Computacion, Facultad de Ingenieria y Arquitectura, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Giraldo, O. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Rosales-Rivera, A., E-mail: arosalesr@unal.edu.co [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia)

    2012-08-15

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn{sup 4+} to Mn{sup 3+}. VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  17. Estimation of cobalt release from feed water heater tubes of BWRs

    International Nuclear Information System (INIS)

    Uchida, S.; Kitamura, M.; Ozawa, Y.

    1983-01-01

    To evaluate the release source of cobalt from heater tubes of the feed water line, release rate measurements were carried out by detecting 60 Co released from irradiated stainless steel in contact with neutral water at an oxygen concentration of 20 ppb. The dependences of cobalt release rate on temperature, flow velocity and exposure time were studied after 670 hours of release experiments, and an empirical equation (which is presented) was obtained in the temperature range from 150 to 240 deg C. A decrease in the cobalt release rate above 250 deg C was considered due to the formation of a protective oxide layer. From these data, the amount of cobalt released from individual feed water heaters was evaluated. It was demonstrated that low cobalt containing stainless steel was economically applied only in the higher temperature region of the heater (20% of the total surface) to reduce cobalt feed rate into the reactor (to approx. 1/2). (author)

  18. Genome-Wide Association Mapping of Crown Rust Resistance in Oat Elite Germplasm.

    Science.gov (United States)

    Klos, Kathy Esvelt; Yimer, Belayneh A; Babiker, Ebrahiem M; Beattie, Aaron D; Bonman, J Michael; Carson, Martin L; Chong, James; Harrison, Stephen A; Ibrahim, Amir M H; Kolb, Frederic L; McCartney, Curt A; McMullen, Michael; Fetch, Jennifer Mitchell; Mohammadi, Mohsen; Murphy, J Paul; Tinker, Nicholas A

    2017-07-01

    Oat crown rust, caused by f. sp. , is a major constraint to oat ( L.) production in many parts of the world. In this first comprehensive multienvironment genome-wide association map of oat crown rust, we used 2972 single-nucleotide polymorphisms (SNPs) genotyped on 631 oat lines for association mapping of quantitative trait loci (QTL). Seedling reaction to crown rust in these lines was assessed as infection type (IT) with each of 10 crown rust isolates. Adult plant reaction was assessed in the field in a total of 10 location-years as percentage severity (SV) and as infection reaction (IR) in a 0-to-1 scale. Overall, 29 SNPs on 12 linkage groups were predictive of crown rust reaction in at least one experiment at a genome-wide level of statistical significance. The QTL identified here include those in regions previously shown to be linked with seedling resistance genes , , , , , and and also with adult-plant resistance and adaptation-related QTL. In addition, QTL on linkage groups Mrg03, Mrg08, and Mrg23 were identified in regions not previously associated with crown rust resistance. Evaluation of marker genotypes in a set of crown rust differential lines supported as the identity of . The SNPs with rare alleles associated with lower disease scores may be suitable for use in marker-assisted selection of oat lines for crown rust resistance. Copyright © 2017 Crop Science Society of America.

  19. A novel method to synthesize cobalt oxide (Co3O4) nanowires from cobalt (Co) nanobowls

    DEFF Research Database (Denmark)

    Srivastava, Akhilesh Kumar; Madhavi, S.; Ramanujan, R.V.

    2010-01-01

    A novel method suitable for the synthesis of the cobalt oxide (Co3O4) nanowires at targeted regions is presented in this report. Cobalt (Co) nanobowls synthesized by colloidal crystal directed assembly were transformed into Co3O4 nanowires by a simple heat treatment process. Co nanobowls exhibited...... a two phase (h.c.p. + f.c.c.) microstructure while single phase microstructure was observed for Co3O4 nanowires. Ferromagnetic Co nanobowls showed a dependence of coercivity on bowl size while Co3O4 exhibited weak ferromagnetic behavior....

  20. A review of cobalt adsorption on transition metal oxides

    International Nuclear Information System (INIS)

    Walker, S.M.

    1987-04-01

    This report reviews studies of cobalt adsorption on transition metal oxides, in the context of corrosion product and radioactivity transport in PWR primary circuits. In general, uptake of cobalt increases with pH, with temperature and with decreasing ionic strength. Very little data are available under PWR primary circuit conditions, but the limited data available suggest that cobalt uptake by the zirconium oxide corrosion product layer on fuel pins may be significant compared to that deposited on fuel crud. If fuel crud levels can be reduced in future by coolant chemistry control then uptake by the zirconia will assume a greater relative role. It is planned to use an autoclave to study uptake of cobalt on oxidised Zircaloy surfaces at temperatures up to 593K under PWR primary circuit chemistry conditions. (author)

  1. Ion exchange of Cobalt and Cadmium in Zeolite X

    International Nuclear Information System (INIS)

    Nava M, I.

    1994-01-01

    The growing development in the industry has an important contribution to the environmental damage, where the natural effluents are each day more contaminated by toxic elements, such as: mercury, chromium, lead and cadmium. So as to separate such elements it has sorbent must have enough stability, and have a sharp capacity of sorption. In this work it was studied the sorption behavior of cobalt and on the other hand, cadmium in aqueous solutions, which along with sodic form of the Zeolite X, undergoes a phenomenon of ionic interchange. Such interchange was verify to different concentration of cadmium, cobalt and hydronium ion. The content of cobalt and sodium in the interchanged samples was detected through the neutronic activation analysis. The results disclose a higher selectivity for cadmium than cobalt. (Author)

  2. The Application of Moessbauer Emission Spectroscopy to Industrial Cobalt Based Fischer-Tropsch Catalysts

    International Nuclear Information System (INIS)

    Loosdrecht, J. van de; Berge, P. J. van; Craje, M. W. J.; Kraan, A. M. van der

    2002-01-01

    The application of Moessbauer emission spectroscopy to study cobalt based Fischer-Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Moessbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer-Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co 3+ species was observed as well as the formation of irreducible Co 3+ and Co 2+ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Moessbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer-Tropsch catalysts under realistic synthesis conditions.

  3. Zirconia crowns for rehabilitation of decayed primary incisors: an esthetic alternative.

    Science.gov (United States)

    Ashima, G; Sarabjot, K Bhatia; Gauba, K; Mittal, H C

    2014-01-01

    Esthetic management of extensively decayed primary maxillary anterior teeth requiring full coronal coverage restoration is usually challenging to the pediatric dentists especially in very young children. Many esthetic options have been tried over the years each having its own advantages, disadvantages and associated technical, functional or esthetic limitations. Zirconia crowns have provided a treatment alternative to address the esthetic concerns and ease of placement of extra-coronal restorations on primary anterior teeth. The present article presents a case where grossly decayed maxillary primary incisors were restored esthetically and functionally with ready made zirconia crowns (ZIRKIZ, HASS Corp; Korea). After endodontic treatment the decayed teeth were restored with zirconia crowns. Over a 30 months period, the crowns have demonstrated good retention and esthetic results. Dealing with esthetic needs in children with extensive loss of tooth structure, using Zirconia crowns would be practical and successful. The treatment described is simple and effective and represents a promising alternative for rehabilitation of decayed primary teeth.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

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

    Science.gov (United States)

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

    2016-07-01

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

  6. Plasma sprayed samarium--cobalt permanent magnets

    International Nuclear Information System (INIS)

    Willson, M.C.; Janowiecki, R.J.

    1975-01-01

    Samarium--cobalt permanent magnets were fabricated by arc plasma spraying. This process involves the injection of relatively coarse powder particles into a high-temperature gas for melting and spraying onto a substrate. The technique is being investigated as an economical method for fabricating cobalt--rare earth magnets for advanced traveling wave tubes and cross-field amplifiers. Plasma spraying permits deposition of material at high rates over large areas with optional direct bonding to the substrate, and offers the ability to fabricate magnets in a variety of shapes and sizes. Isotropic magnets were produced with high coercivity and good reproducibility in magnetic properties. Post-spray thermal treatments were used to enhance the magnetic properties of sprayed deposits. Samarium--cobalt magnets, sprayed from samarium-rich powder and subjected to post-spray heat treatment, displayed energy products in excess of 9 million gauss-oersteds and coercive forces of approximately 6000 oersteds. Bar magnet arrays were constructed by depositing magnets on ceramic substrates. (auth)

  7. The cobalt radioactive isotopes in environment

    International Nuclear Information System (INIS)

    2007-01-01

    For the year 1993 the total activity released in cobalt is 69 GBq for the whole of nuclear power plants. The part of activity in cobalt for La Hague in 1993 is 8 GBq of 58 Co and 2 GBq of 60 Co. The radioactive isotopes released by nuclear power plants or the reprocessing plant of La Hague under liquid effluents are shared by half between 58 Co and 60 Co. The exposure to sealed sources is the most important risk for the cobalt. The risk of acute exposure can associate a local irradiation of several decades of grays inducing a radiological burns, deep burn to treat in surgery by resection or graft even amputation. A global irradiation of organism for several grays induces an acute irradiation syndrome, often serious. At long term the stochastic effects are represented by leukemia and radio-induced cancers. The increase of probability of their occurrence is 1% by sievert. We must remind that the natural spontaneous probability is 25%. (N.C.)

  8. Calculation support for industrial production of cobalt-60 at Leningrad NPP

    International Nuclear Information System (INIS)

    Artemov, Vladimir; Elshin, Alexander; Ivanov, Alexander; Gorbunov, Evgeny; Ikonnikov, Roman; Pimenov, Alexander

    2008-01-01

    Cobalt-60 is industrially produced at the Leningrad NPP by irradiation of cobalt-59 in special-purpose facilities loaded into the RBMK reactor core (all 4 units). The paper describes calculation methods used to determine the current activity of cobalt in irradiation assemblies for their timely unloading. The described peculiarities of core calculation model account for continuous refueling, overloading of irradiation assemblies and individual thermohydraulics in each channel under variation of reactor power. Fuel burnup in the core is calculated with a time step of about 24 hours. The resulting values for cobalt activity and uncertainties are presented in the paper as well. Deviation of calculated cobalt activity from measured activity is within the experimental accuracy of 10% (at confidence probability of 0.95). (authors)

  9. Sorption behavior of cobalt on manganese dioxide, smectite and their mixture

    International Nuclear Information System (INIS)

    Ohnuki, T.; Kozai, N.

    1995-01-01

    The sorption behavior of cobalt on manganese dioxide, the clay mineral smectite and mixtures of the two was studied by batch type sorption/desorption experiments at neutral pH. Sorption behavior was examined by sequential extraction, in which the sorbents were contacted first with a 1 M CH 3 COONH 4 solution and then with a hydroxylamine solution (NH 2 OH of 1 M with 25 weight % CH 3 COOH). More than 70% of the sorbed cobalt was desorbed from smectite with a 1 M CH 3 COONH 4 solution: about 15% of the cobalt remained on the smectite after treatment with the hydroxylamine solution. Less than 1% of the remaining cobalt was desorbed from manganese dioxide with a 1 M CH 3 COONH 4 solution; with the hydroxylamine solution, all was desorbed. In mixtures of MnO 2 and smectite that were formulated to sorb equal amounts of cobalt regardless of the MnO 2 /smectite ratio in the mixture, less than 5% of the sorbed cobalt was desorbed by treatment with 1 M CH 3 COONH 4 . The fraction of the cobalt desorbed by treatment with the hydroxylamine solution increased with increased MnO 2 in the mixtures. The fraction of the cobalt sorbed on MnO 2 in the mixture was estimated from the desorption experiments. The results showed that higher fractions were sorbed onto MnO 2 than were estimated by the weighted averages of distribution coefficients for MnO 2 and smectite. Therefore, in minerals of the mixture, manganese dioxide is a more important component than smectite for the sorption of cobalt. (orig.)

  10. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2016-08-11

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  11. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  12. Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Pápai, Mátyás Imre; Penfold, Thomas J.; Møller, Klaus Braagaard

    2016-01-01

    -vibronic quantum dynamics simulations on the Fe-N-heterocyclic carbene complex, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe(bmip)2]2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene....... This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck-Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet...

  13. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, Motokazu; Koyanagi, Taku; Saiki, Masamichi

    1976-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link of food chain in the sea. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer expts. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26 through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (auth.)

  14. Concentration of radioactive cobalt by seaweeds in the food chain

    International Nuclear Information System (INIS)

    Nakahara, M.; Koyanagi, T.; Saiki, M.

    1975-01-01

    On the pathway of radioactive substances in marine environments, seaweeds play an important role because of their higher concentration factors for many radionuclides and because they constitute a link in the food chain. In the present work, uptake, distribution and excretion of radioactive cobalt were studied on several kinds of seaweeds by radioisotope tracer experiments under laboratory conditions and concentration factors were calculated. The concentration factors were also estimated from the results of stable cobalt determination by activation analysis or atomic absorption spectrometry on seaweeds and seawater, and compared with the results of tracer experiments. The seaweeds showed the species specificity for the concentration of stable and radioactive cobalt with diverse values of concentration factors and biological half-lives. The transfer of radioactive cobalt in the food chain from contaminated seaweeds to mollusca was examined by feeding abalones, Haliotis discus, with four kinds of seaweed labelled with 60 Co and observing retention. Absorption rate for radioactive cobalt by abalones calculated at two days after feeding showed diverse values depending upon the species of seaweed, as follows: 47% through Laminaria japonica and Ulva pertusa, 31% through Undaria pinnatifida and 26% through Eisenia bicyclis, respectively. From the results, it was assumed that the accumulation of radioactive cobalt by mollusca is affected by the species of seaweeds as food. A very high concentration of ingested radioactive cobalt in the midgut gland was seen on the autoradiograph of abalone samples. (author)

  15. 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.

  16. PENYERAPAN COBALT-60 DARI AIR OLEH TANAMAN KIAPU (Pistia stratiotes L.)

    OpenAIRE

    Lailatul Nuzzulul Safitri; Poppy Intan Tjahaja; Ida Bagus Made Suryatika

    2015-01-01

    Has conducted research Cobalt-60 radionuclide uptake by plants kiapu (Pistia stratiotes L.) found in many waters. The purpose of the study was to determine the value of the transfer factor on plant kiapu to Cobalt-60 in water. The study was conducted by growing plants on media kiapu gutter water in pots with the height 35 cm and diameter 11,5 cm containing Cobalt-60. The amount of Cobalt - 60 is absorbed and accumulated by the plant parts, i.e. roots and leaves, was observed by measuring the ...

  17. The structural evolution and diffusion during the chemical transformation from cobalt to cobalt phosphide nanoparticles

    KAUST Repository

    Ha, Don-Hyung

    2011-01-01

    We report the structural evolution and the diffusion processes which occur during the phase transformation of nanoparticles (NPs), ε-Co to Co 2P to CoP, from a reaction with tri-n-octylphosphine (TOP). Extended X-ray absorption fine structure (EXAFS) investigations were used to elucidate the changes in the local structure of cobalt atoms which occur as the chemical transformation progresses. The lack of long-range order, spread in interatomic distances, and overall increase in mean-square disorder compared with bulk structure reveal the decrease in the NP\\'s structural order compared with bulk structure, which contributes to their deviation from bulk-like behavior. Results from EXAFS show both the Co2P and CoP phases contain excess Co. Results from EXAFS, transmission electron microscopy, X-ray diffraction, and density functional theory calculations reveal that the inward diffusion of phosphorus is more favorable at the beginning of the transformation from ε-Co to Co2P by forming an amorphous Co-P shell, while retaining a crystalline cobalt core. When the major phase of the sample turns to Co 2P, the diffusion processes reverse and cobalt atom out-diffusion is favored, leaving a hollow void, characteristic of the nanoscale Kirkendall effect. For the transformation from Co2P to CoP theory predicts an outward diffusion of cobalt while the anion lattice remains intact. In real samples, however, the Co-rich nanoparticles continue Kirkendall hollowing. Knowledge about the transformation method and structural properties provides a means to tailor the synthesis and composition of the NPs to facilitate their use in applications. © 2011 The Royal Society of Chemistry.

  18. Development of hierarchically porous cobalt oxide for enhanced photo-oxidation of indoor pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, J. P., E-mail: chengjp@zju.edu.cn [Zhejiang University, State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering (China); Shereef, Anas; Gray, Kimberly A., E-mail: k-gray@northwestern.edu [Northwestern University, Center for Catalysis and Surface Science (United States); Wu, Jinsong [Northwestern University, Department of Materials Science and Engineering (United States)

    2015-03-15

    Porous cobalt oxide was successfully prepared by precipitation of cobalt hydroxide followed by low temperature thermal decomposition. The morphologies of the resultant oxides remained as the corresponding hydroxides, although the morphology of cobalt hydroxides was greatly influenced by the precursor salts. The cobalt oxides with average crystal size less than 20 nm were characterized by X-ray diffraction, scanning electron microscope, BET surface area, and XPS analysis. The photocatalytic activities of the various cobalt oxides morphologies were investigated by comparing the photo-degradation of acetaldehyde under simulated solar illumination. Relative to their low order structures and reference titania samples, the hierarchical nanostructures of cobalt oxide showed excellent abilities to rapidly degrade acetaldehyde, a model air pollutant. This was attributed to the unique nature of these hierarchical cobalt oxide nanoassemblies, which contained many catalytically active reaction sites and open pores.

  19. Substoichiometric cobalt oxide monolayer on Ir(100)-(1 x 1)

    International Nuclear Information System (INIS)

    Gubo, M; Ebensperger, C; Meyer, W; Hammer, L; Heinz, K

    2009-01-01

    A substoichiometric monolayer of cobalt oxide has been prepared by deposition and oxidation of slightly less than one monolayer of cobalt on the unreconstructed surface of Ir(100). The ultrathin film was investigated by scanning tunnelling microscopy (STM) and quantitative low-energy electron diffraction (LEED). The cobalt species of the film reside in or near hollow positions of the substrate with, however, unoccupied sites (vacancies) in a 3 x 3 arrangement. In the so-formed 3 x 3 supercell the oxide's oxygen species are both threefold and fourfold coordinated to cobalt, forming pyramids with a triangular and square cobalt basis, respectively. These pyramids are the building blocks of the oxide. Due to the reduced coordination as compared to the sixfold one in the bulk of rock-salt-type CoO, the Co-O bond lengths are smaller than in the latter. For the threefold coordination they compare very well with the bond length in oxygen terminated CoO(111) films investigated recently. The substoichiometric 3 x 3 oxide monolayer phase transforms to a stoichiometric c(10 x 2)-periodic oxide monolayer under oxygen exposure, in which, however, cobalt and oxygen species are in (111) orientation and so form a CoO(111) layer.

  20. 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.

  1. Telescopic crowns as attachments for implant supported restorations: a case series.

    Science.gov (United States)

    Hoffmann, Oliver; Beaumont, Christian; Tatakis, Dimitris N; Zafiropoulos, Gregory-George

    2006-01-01

    The use of dental implants to support mandibular or maxillary overdentures is a widely used treatment modality. Advantages are an increase in retention, an increase in chewing ability, and easy access for oral hygiene procedures. While telescopic and conical crowns have been used for decades to connect natural teeth to overdentures, not many cases have been reported in the literature of telescopic crowns placed on implants to support overdentures. This article describes 7 patients with overdentures supported by telescopic crowns who received 65 implants (ITI Straumann). The cases presented in this report have been in function for up to 4.5 years. During that time no adverse events were reported. The use of telescopic crowns as attachments for implant-supported overdentures may be a viable treatment option.

  2. {alpha},{beta}-Unsaturated Fischer carbene complexes as chemical multitalents

    Energy Technology Data Exchange (ETDEWEB)

    Meijere, A. de [Institut fuer Organische Chemie der George-August-Universitaet Goettingen (Germany)

    1995-12-31

    The well established reaction of {alpha},{beta}-unsaturated Fischer carbenechromium complexes 6(R{sup 1} = H) with alkynes normally proceeds with carbonyl insertion to yield 4-alkoxyphenols 9. Led by the incidental formation of a cyclopentadiene 3 from certain {beta}-aminosubstituted complexes 6(X = NR{sub 2}{sup 3}, R{sup 1} = cPr) the authors have studied the influences of the nature of substituents (R{sup 1}, X on 6; R{sub L}, R{sub S} in the alkyne; R{sup 3} in the amino group), solvents, and temperature on the outcome of the reaction. Imino substitution on complexes 6 leads to 2H-pyrroles 1, a free primary amino group (X = NH{sub 2}) to pyridines 5, and bulky substituents R{sup 1} to cyclopenta[b]pyrans 8 with double insertion of an alkyne. Eventually, appropriate conditions have been developed which permit to selectively prepare either 3-alkoxy-5-(dialkylamino)cyclopentadienes 3 (as synthetic equivalents of cyclopentenones 4), 5-(dialkylaminomethylene)cyclopent-2-enones 7, 3-alkoxy-2-(1{prime}-morpholino-1{prime}-alkenyl)cyclopent-2-enones 10, and 2-acyl-3-(dialkylamino)cyclopent-2-enones 11 from easily accessible carbene complexes 6 (X = NR{sub 2}{sup 3}) in high yields. Mechanistic aspects and implications of these novel transformations will be discussed.

  3. Testing of cobalt-free alloys for valve applications using a special test loop

    International Nuclear Information System (INIS)

    Benhamou, C.

    1992-01-01

    Considering that use of cobalt alloys should be avoided as far as possible in PWR components, a programme aimed at establishing the performance of cobalt-free alloys has been performed for valve applications, where cobalt alloys are mainly used. Referring to past work, two types of cobalt-free alloys were selected: Ni-Cr-B-Si and Ni-Cr-Fe alloys. Cobalt-free valves' behaviour has been evaluated comparatively with cobalt valves by implementation of a programme in a special PWR test loop. At the issue of the loop test programme, which included endurance, thermal shock and erosion tests, cobalt-free alloys candidate to replace cobalt alloys are proposed in relation with valve type (globe valve and swing check valve). The following was established: (i) Colmonoy 4-26 (Ni-Cr-B-Si alloy) and Cenium Z20 (Ni-Cr-Fe alloy) deposited by plasma arc process were found suitable for use in 3inch swing check valves; (ii) for integral parts acting as guide rings, Nitronic 60 and Cesium Z20/698 were tested successfully; (iii) for small-bore components such as 2inch globe valves, no solution can yet be proposed; introduction of cobalt-free alloys is dependent on the development of automatic advanced arc surfacing techniques applied to small-bore components

  4. Neutron diffraction studies on cobalt substituted BiFeO3

    Science.gov (United States)

    Ray, J.; Biswal, A. K.; Acharya, S.; Babu, P. D.; Siruguri, V.; Vishwakarma, P. N.

    2013-02-01

    A dilute concentration of single phase Cobalt substituted Bismuth ferrite, BiFe1-XCoXO3; (x=0, 0.02) is prepared by sol-gel auto combustion method. Room temperature neutron diffraction patterns show no change in the crystal and magnetic structure upon cobalt doping. The calculation of magnetic moments shows 3.848 μB for Fe+ and 2.85 μB for Co3+. The cobalt is found to be in intermediate spin state.

  5. Clinical performance - a reflection of damage accumulation in ceramic dental crowns

    Energy Technology Data Exchange (ETDEWEB)

    Rekow, D.E. [Univ. of Medicine and Dentistry of New Jersey, Newark, NJ (United States). Dept. of Orthodontics; Thompson, V.P. [Univ. of Medicine and Dentistry of New Jersey, Newark, NJ (United States). New Jersey Dental School

    2001-07-01

    All-ceramic dental crowns have tremendous appeal for patients - their esthetics nearly match those of natural teeth. Unfortunately, the most esthetic materials are brittle and, consequently, are vulnerable to damage relating to shaping which is exacerbated during cyclic loading during normal chewing. Clinical performance of all-ceramic dental prostheses are directly dependent on damage introduced during fabrication and during fatigue loading associated with function. The accumulation of damage results in unacceptably high failure rates (where failure is defined as a complete fracture requiring replacement of the prosthesis). The relation between shaping damage and fatigue damage on clinical performance of all-ceramic dental crowns was investigated. Materials used commercially for all-ceramic crowns and investigated in this study included a series of different microstructures of machinable glass ceramics (Corning), aluminas and porcelains (Vita Zahnfabrik), and zirconia (Norton). As monolithic materials, strong, tough, fatigue-resistant materials are not sufficiently esthetic for crowns. Crowns fabricated from monolithic esthetic materials have high failure rates. Layering ceramics could provide acceptable strength through management of damage accumulation. (orig.)

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

    Science.gov (United States)

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

    2006-01-01

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

  7. [Comparative adaptation of crowns of selective laser melting and wax-lost-casting method].

    Science.gov (United States)

    Li, Guo-qiang; Shen, Qing-yi; Gao, Jian-hua; Wu, Xue-ying; Chen, Li; Dai, Wen-an

    2012-07-01

    To investigate the marginal adaptation of crowns fabricated by selective laser melting (SLM) and wax-lost-casting method, so as to provide an experimental basis for clinic. Co-Cr alloy full crown were fabricated by SLM and wax-lost-casting for 24 samples in each group. All crowns were cemented with zinc phosphate cement and cut along longitudinal axis by line cutting machine. The gap between crown tissue surface and die was measured by 6-point measuring method with scanning electron microscope (SEM). The marginal adaptation of crowns fabricated by SLM and wax-lost-casting were compared statistically. The gap between SLM crowns were (36.51 ± 2.94), (49.36 ± 3.31), (56.48 ± 3.35), (42.20 ± 3.60) µm, and wax-lost-casting crowns were (68.86 ± 5.41), (58.86 ± 6.10), (70.62 ± 5.79), (69.90 ± 6.00) µm. There were significant difference between two groups (P casting method and SLM method provide acceptable marginal adaptation in clinic, and the marginal adaptation of SLM is better than that of wax-lost-casting method.

  8. The general properties of water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction systems

    International Nuclear Information System (INIS)

    Vanura, P.

    2003-01-01

    The extraction and stability constants in the system water - nitrobenzene have been collected and general rules valid for water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction system have been found. The main principles are size compatibility of ion diameter and crown cavity diameters, the flexibility of crown, the basicity of crown and the steric factor of both the ligand and the extracted ion. The extraction in the system water - mineral acid or salt polyoxyethylene compound - bis-1,2-dicarbollylcobaltate - nitrobenzene is more complicated than can be expected from usually used ion diameter - crown cavity diameter compatibility principle. The other important factors are the basicity and the deformability of crown, steric aspect and the angles of bonds of extracted ion. The binuclear 'sandwich' complexes with H + ion and Sr 2+ or Ba 2+ ions have been proved for dibenzo-18-crown-6 (DB18C6). On the other hand, only SrL 2 and BaL 2 (L = 15C5) complexes are formed in nitrobenzene saturated with water. The addition of polyoxyethylene compound usually increases the distribution ratio of alkali earth metal ions and the selectivity of its mutual separation. (authors)

  9. Construction of an apparatus for nuclear orientation measurements at low temperatures. Application to neodymium-cobalt alloy; Realisation d'un appareil pour des mesures d'orientation nucleaire a basse temperature. Application a l'alliage neodyme-cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Mayer, E [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1965-10-01

    We describe experiments along which has been studied the anisotropy of {gamma} radiations emitted by oriented nuclei. We have used the great hyperfine fields acting on nuclei in ferromagnetic metals so as to produce alignment at low temperature. By irradiation we obtained a few cobalt 60 nuclei in our samples which were then cooled down to 0,01 K. The anisotropic rate of the 1,33 MeV {gamma} radiation was measured in function of the sample temperature, using as thermometer the anisotropy of {gamma} radiation emitted by cobalt 60 nuclei in a cobalt single crystal. Cobalt 60 was lined up in a cobalt nickel alloy (40% Ni). The hyperfine field at the cobalt was measured compared to the effective field in metallic cobalt: Heff(Co Ni)/Heff(Co metal) = 0.71 {+-} 0.12. These results are in good agreement with specific heat measurements made previously. Cobalt 60 has been polarised in a neodymium-cobalt alloy (NdCo{sub 5}). The field at the cobalt in NdCo{sub 5} has been measured compared to the field in metallic cobalt and taking the non-saturation into account we found 165000 oersteds < Heff(NdCo{sub 5}) < 220000 oersteds. (author) [French] Nous decrivons des experiences au cours desquelles nous avons etudie l'anisotropie de rayonnements {gamma} emis par des noyaux orientes. Nous avons utilise les grands champs hyperfins agissant sur las noyaux dans les metaux ferromagnetiques pour produire l'alignement a basse temperature. Par irradiation nous avons obtenu quelques noyaux de cobalt 60 dans nos echantillons qui furent ensuite refroidis a 0,01 K. Le degre d'anisotropie du rayonnement {gamma} de 1,33 MeV fut mesure en fonction de la temperature de l'echantillon en utilisant l'anisotropie du rayonnement {gamma} de noyaux de cobalt 60 dans un monocristal de cobalt metallique utilise comme thermometre. Le cobalt 60 a ete aligne dans un alliage de cobalt-nickel (40% Ni). Le champ hyperfin au niveau du cobalt a ete mesure par rapport au champ effectif dans le cobalt metallique

  10. Fit of interim crowns fabricated using photopolymer-jetting 3D printing.

    Science.gov (United States)

    Mai, Hang-Nga; Lee, Kyu-Bok; Lee, Du-Hyeong

    2017-08-01

    The fit of interim crowns fabricated using 3-dimensional (3D) printing is unknown. The purpose of this in vitro study was to evaluate the fit of interim crowns fabricated using photopolymer-jetting 3D printing and to compare it with that of milling and compression molding methods. Twelve study models were fabricated by making an impression of a metal master model of the mandibular first molar. On each study model, interim crowns (N=36) were fabricated using compression molding (molding group, n=12), milling (milling group, n=12), and 3D polymer-jetting methods. The crowns were prepared as follows: molding group, overimpression technique; milling group, a 5-axis dental milling machine; and polymer-jetting group using a 3D printer. The fit of interim crowns was evaluated in the proximal, marginal, internal axial, and internal occlusal regions by using the image-superimposition and silicone-replica techniques. The Mann-Whitney U test and Kruskal-Wallis tests were used to compare the results among groups (α=.05). Compared with the molding group, the milling and polymer-jetting groups showed more accurate results in the proximal and marginal regions (P3D printing significantly enhanced the fit of interim crowns, particularly in the occlusal region. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  11. Bioactivity and mechanical behaviour of cobalt oxide-doped ...

    Indian Academy of Sciences (India)

    tive base glass and cobalt oxide-doped glass were prepared by the addition of cobalt oxide (0, ... and 1 N HCl at 37. ◦. C as compared with the ... SO2−. 4. Cl. −. Simulated body fluid. 142.0. 5.0. 1.5. 2.5. 4.2. 1.0. 0.5. 147.8. Human blood plasma ...

  12. Comparative in vitro evaluation of CAD/CAM vs conventional provisional crowns.

    Science.gov (United States)

    Abdullah, Adil Othman; Tsitrou, Effrosyni A; Pollington, Sarah

    2016-01-01

    This study compared the marginal gap, internal fit, fracture strength, and mode of fracture of CAD/CAM provisional crowns with that of direct provisional crowns. An upper right first premolar phantom tooth was prepared for full ceramic crown following tooth preparation guidelines. The materials tested were: VITA CAD-Temp®, Polyetheretherketone "PEEK", Telio CAD-Temp, and Protemp™4 (control group). The crowns were divided into four groups (n=10), Group1: VITA CAD-Temp®, Group 2: PEEK, Group 3: Telio CAD-Temp, and Group 4: Protemp™4. Each crown was investigated for marginal and internal fit, fracture strength, and mode of fracture. Statistical analysis was performed using GraphPad Prism software version 6.0. The average marginal gap was: VITA CAD-Temp® 60.61 (±9.99) µm, PEEK 46.75 (±8.26) µm, Telio CAD-Temp 56.10 (±5.65) µm, and Protemp™4 193.07(±35.96) µm (PCAD-Temp® 124.94 (±22.96) µm, PEEK 113.14 (±23.55) µm, Telio CAD-Temp 110.95 (±11.64) µm, and Protemp™4 143.48(±26.74) µm. The average fracture strength was: VITA CAD-Temp® 361.01 (±21.61) N, PEEK 802.23 (±111.29) N, Telio CAD-Temp 719.24 (±95.17) N, and Protemp™4 416.40 (±69.14) N. One-way ANOVA test showed a statistically significant difference for marginal gap, internal gap, and fracture strength between all groups (p0.05). CAD/CAM fabricated provisional crowns demonstrated superior fit and better strength than direct provisional crowns.

  13. Fracture strength testing of crowns made of CAD/CAM composite resins.

    Science.gov (United States)

    Okada, Ryota; Asakura, Masaki; Ando, Akihiro; Kumano, Hirokazu; Ban, Seiji; Kawai, Tatsushi; Takebe, Jun

    2018-03-28

    The purpose of this study was to ascertain whether computer aided design/computer aided manufacturing (CAD/CAM) composite resin crowns have sufficient strength to withstand the bite force of the molar teeth. The null hypothesis was that the fracture strength of CAD/CAM composite resin crowns is lower than the average maximum bite force of the molar tooth. The crowns, which shape is the right maxillary first molar, were fabricated using four CAD/CAM blanks made of composite resins (Block HC: HC, KZR-CAD HR: HR, KZR-CAD HR2: HR2, Avencia Block: AVE) and one CAD/CAM blank made of lithium disilicate glass-ceramic (IPS e.max CAD: IPS), which was used as a control. Fracture strength of fabricated crowns bonded to metal abutment and biaxial flexural strength of the materials were evaluated. The results of fracture strength test and biaxial flexural strength test showed different tendencies. The fracture strength of CAD/CAM composite resin crowns except HC ranged from 3.3kN to 3.9kN, and was similar to that of IPS (3.3kN). In contrast, biaxial flexural strength of CAD/CAM composite resins ranged from 175MPa to 247MPa, and was significantly lower than that of IPS (360MPa). All CAD/CAM composite resin crowns studied presented about 3-4 times higher fracture strength than the average maximum bite force of the molar tooth (700-900N), which result leads to the conclusion that CAD/CAM composite resin crowns would have sufficient strength to withstand the bite force of the molar teeth. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  14. Cobalt production in RAPS-1

    International Nuclear Information System (INIS)

    Krishnan, P.D.; Purandare, H.D.

    1978-01-01

    At present in RAPS-1 radioisotope Co 60 is produced by irradiating Co 59 in the adjusters which perform the function of regulation of reactivity, power and xenon override. But the manrem expenditure of the crew handling the charge and discharge of the adjusters is going to be prohibitively high. It is therefore proposed to irradiate Co 59 in the fuel channel positions. The physics optimisation study for such irradiation is presented. The burnup penalty and loss of power are estimated to produce the required quantity of Co 60 after optimising the number of cobalt pencils in a bundle and the positions of the cobalt producing channels in the reactor core. (author)

  15. Nickel and cobalt bimetallic hydroxide catalysts for urea electro-oxidation

    International Nuclear Information System (INIS)

    Yan Wei; Wang Dan; Botte, Gerardine G.

    2012-01-01

    Nickel–Cobalt bimetallic hydroxide electrocatalysts, synthesized through a one-step electrodeposition method, were evaluated for the oxidation of urea in alkaline conditions with the intention of reducing the oxidation overpotential for this reaction. The Nickel–Cobalt bimetallic hydroxide catalysts were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Raman spectroscopy, cyclic voltammetry (CV), and polarization techniques. A significant reduction in the overpotential (150 mV) of the reaction was observed with the Nickel–Cobalt bimetallic hydroxide electrode (ca. 43% Co content) when compared to a nickel hydroxide electrode. The decrease of the urea oxidation potential on the Nickel–Cobalt bimetallic hydroxide electrodes reveals great potential for future applications of urea electro-oxidation, including wastewater remediation, hydrogen production, sensors, and fuel cells.

  16. Radium separation through complexation by aqueous crown ethers and ion exchange or solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Chiarizia, R.; Dietz, M.L.; Horwitz, E.P. [Argonne National Lab., IL (United States). Chemistry Div.; Burnett, W.C. [Florida State Univ., Tallahassee, FL (United States). Dept. of Oceanography

    1997-11-01

    The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-crown-7 (21C7)) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium-calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes is discussed and a possible flowchart for the determination of {sup 226}Ra/{sup 228}Ra in natural waters is presented.

  17. Influence of coping design on the cervical color of ceramic crowns.

    Science.gov (United States)

    Paniz, Gianluca; Kang, Ki-Ho; Kim, Yongjeong; Kumagai, Naota; Hirayama, Hiroshi

    2013-12-01

    The replication of natural teeth, especially with single-tooth restorations, represents a challenge. Similar to metal ceramic crowns, different designs of zirconia substructures have been suggested to improve the esthetic results of zirconia ceramic crowns. The purpose of the study was to analyze the color of the cervical portion of single zirconia ceramic crowns fabricated with different zirconia coping designs. The color, measured on the CIELAB color scale, of 3 different groups of restorations (n=10) fabricated with zirconia coping (Lava) and feldspathic porcelain (Noritake Super Porcelain) was analyzed with a spectrophotometer. Conventional zirconia crowns with zirconia facial margins were compared with ceramic crowns with porcelain facial margins and either a horizontal reduction of the zirconia coping (1.0 mm reduction) or an additional vertical reduction (1.0 mm additional reduction). The 3 groups, each with a different coping extension, were examined with a 1-way ANOVA and the Fisher exact test, and the differences of the groups were evaluated by applying ΔE thresholds (α=.05). The mean color difference among all the groups was not clinically significant (ΔEcolor differences were present between the 2 porcelain butt margin groups of crowns (ΔE=1.06, between group H and V). Increased differences were present between the zirconia margin group and the porcelain butt margin group (ΔE=2.54 between group C and H; ΔE=2.41 between group C and V). Lab* values were examined in all the groups of crowns to determine the clinical implications. Within the limitation of the study, no significant differences were present among the tested groups of crowns. Nevertheless, although some differences were present between the zirconia margin group and the porcelain butt margin group, reduced differences were present between the 2 different cutback designs. Copyright © 2013 Editorial Council for the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights

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

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  19. Numerical modeling of laboratory-scale surface-to-crown fire transition

    Science.gov (United States)

    Castle, Drew Clayton

    Understanding the conditions leading to the transition of fire spread from a surface fuel to an elevated (crown) fuel is critical to effective fire risk assessment and management. Surface fires that successfully transition to crown fires can be very difficult to suppress, potentially leading to damages in the natural and built environments. This is relevant to chaparral shrub lands which are common throughout parts of the Southwest U.S. and represent a significant part of the wildland urban interface. The ability of the Wildland-Urban Interface Fire Dynamic Simulator (WFDS) to model surface-to-crown fire transition was evaluated through comparison to laboratory experiments. The WFDS model is being developed by the U.S. Forest Service (USFS) and the National Institute of Standards and Technology. The experiments were conducted at the USFS Forest Fire Laboratory in Riverside, California. The experiments measured the ignition of chamise (Adenostoma fasciculatum) crown fuel held above a surface fire spreading through excelsior fuel. Cases with different crown fuel bulk densities, crown fuel base heights, and imposed wind speeds were considered. Cold-flow simulations yielded wind speed profiles that closely matched the experimental measurements. Next, fire simulations with only the surface fuel were conducted to verify the rate of spread while factors such as substrate properties were varied. Finally, simulations with both a surface fuel and a crown fuel were completed. Examination of specific surface fire characteristics (rate of spread, flame angle, etc.) and the corresponding experimental surface fire behavior provided a basis for comparison of the factors most responsible for transition from a surface fire to the raised fuel ignition. The rate of spread was determined by tracking the flame in the Smokeview animations using a tool developed for tracking an actual flame in a video. WFDS simulations produced results in both surface fire spread and raised fuel bed

  20. Anti-trypanosomal activity of cationic N-heterocyclic carbene gold(I) complexes.

    Science.gov (United States)

    Winter, Isabel; Lockhauserbäumer, Julia; Lallinger-Kube, Gertrud; Schobert, Rainer; Ersfeld, Klaus; Biersack, Bernhard

    2017-06-01

    Two gold(I) N-heterocyclic carbene complexes 1a and 1b were tested for their anti-trypanosomal activity against Trypanosoma brucei parasites. Both gold compounds exhibited excellent anti-trypanosomal activity (IC 50 =0.9-3.0nM). The effects of the gold complexes 1a and 1b on the T. b. brucei cytoskeleton were evaluated. Rapid detachment of the flagellum from the cell body occurred after treatment with the gold complexes. In addition, a quick and complete degeneration of the parasitic cytoskeleton was induced by the gold complexes, only the microtubules of the detached flagellum remained intact. Both gold compounds 1a and 1b feature selective anti-trypanosomal agents and were distinctly more active against T. b. brucei cells than against human HeLa cells. Thus, the gold complexes 1a and 1b feature promising drug candidates for the treatment of trypanosome infections such as sleeping sickness (human African Trypanosomiasis caused by Trypanosoma brucei parasites). Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Fracture strength and failure mode of maxillary implant-supported provisional single crowns: a comparison of composite resin crowns fabricated directly over PEEK abutments and solid titanium abutments.

    Science.gov (United States)

    Santing, Hendrik Jacob; Meijer, Henny J A; Raghoebar, Gerry M; Özcan, Mutlu

    2012-12-01

    Polyetheretherketone (PEEK) temporary abutments have been recently introduced for making implant-supported provisional single crowns. Little information is available in the dental literature on the durability of provisional implant-supported restorations. The objectives of this study were to evaluate the fracture strength of implant-supported composite resin crowns on PEEK and solid titanium temporary abutments, and to analyze the failure types. Three types of provisional abutments, RN synOcta Temporary Meso Abutment (PEEK; Straumann), RN synOcta Titanium Post for Temporary Restorations (Straumann), and Temporary Abutment Engaging NobRplRP (Nobel Biocare) were used, and provisional screw-retained crowns using composite resin (Solidex) were fabricated for four different locations in the maxilla. The specimens were tested in a universal testing machine at a crosshead speed of 1 mm/minute until fracture occurred. The failure types were analyzed and further categorized as irreparable (Type 1) or reparable (Type 2). No significant difference was found between different abutment types. Only for the position of the maxillary central incisor, composite resin crowns on PEEK temporary abutments showed significantly lower (p Provisional crowns on PEEK abutments showed similar fracture strength as titanium temporary abutments except for central incisors. Maxillary right central incisor composite resin crowns on PEEK temporary abutments fractured below the mean anterior masticatory loading forces reported to be approximately 206 N. © 2010 Wiley Periodicals, Inc.

  2. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    Science.gov (United States)

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  3. Crown-Level Tree Species Classification Using Integrated Airborne Hyperspectral and LIDAR Remote Sensing Data

    Science.gov (United States)

    Wang, Z.; Wu, J.; Wang, Y.; Kong, X.; Bao, H.; Ni, Y.; Ma, L.; Jin, J.

    2018-05-01

    Mapping tree species is essential for sustainable planning as well as to improve our understanding of the role of different trees as different ecological service. However, crown-level tree species automatic classification is a challenging task due to the spectral similarity among diversified tree species, fine-scale spatial variation, shadow, and underlying objects within a crown. Advanced remote sensing data such as airborne Light Detection and Ranging (LiDAR) and hyperspectral imagery offer a great potential opportunity to derive crown spectral, structure and canopy physiological information at the individual crown scale, which can be useful for mapping tree species. In this paper, an innovative approach was developed for tree species classification at the crown level. The method utilized LiDAR data for individual tree crown delineation and morphological structure extraction, and Compact Airborne Spectrographic Imager (CASI) hyperspectral imagery for pure crown-scale spectral extraction. Specifically, four steps were include: 1) A weighted mean filtering method was developed to improve the accuracy of the smoothed Canopy Height Model (CHM) derived from LiDAR data; 2) The marker-controlled watershed segmentation algorithm was, therefore, also employed to delineate the tree-level canopy from the CHM image in this study, and then individual tree height and tree crown were calculated according to the delineated crown; 3) Spectral features within 3 × 3 neighborhood regions centered on the treetops detected by the treetop detection algorithm were derived from the spectrally normalized CASI imagery; 4) The shape characteristics related to their crown diameters and heights were established, and different crown-level tree species were classified using the combination of spectral and shape characteristics. Analysis of results suggests that the developed classification strategy in this paper (OA = 85.12 %, Kc = 0.90) performed better than LiDAR-metrics method (OA = 79

  4. Sintered cobalt-rare earth intermetallic product

    International Nuclear Information System (INIS)

    Benz, M.C.

    1975-01-01

    A process is described for preparing novel sintered cobalt--rare earth intermetallic products which can be magnetized to form permanent magnets having stable improved magnetic properties. A cobalt--rare earth metal alloy is formed having a composition which at sintering temperature falls outside the composition covered by the single Co 5 R intermetallic phase on the rare earth richer side. The alloy contains a major amount of the Co 5 R intermetallic phase and a second solid CoR phase which is richer in rare earth metal content than the Co 5 R phase. The specific cobalt and rare earth metal content of the alloy is substantially the same as that desired in the sintered product. The alloy, in particulate form, is pressed into compacts and sintered to the desired density. The sintered product is comprised of a major amount of the Co 5 R solid intermetallic phase and up to about 35 percent of the product of the second solid CoR intermetallic phase which is richer in rare earth metal content than the Co 5 R phase

  5. Hot corrosion of low cobalt alloys

    Science.gov (United States)

    Stearns, C. A.

    1982-01-01

    The hot corrosion attack susceptibility of various alloys as a function of strategic materials content are investigated. Preliminary results were obtained for two commercial alloys, UDIMET 700 and Mar-M 247, that were modified by varying the cobalt content. For both alloys the cobalt content was reduced in steps to zero. Nickel content was increased accordingly to make up for the reduced cobalt but all other constituents were held constant. Wedge bar test samples were produced by casting. The hot corrosion test consisted of cyclically exposing samples to the high velocity flow of combustion products from an air-fuel burner fueled with jet A-1 and seeded with a sodium chloride aqueous solution. The flow velocity was Mach 0.5 and the sodium level was maintained at 0.5 ppm in terms of fuel plus air. The test cycle consisted of holding the test samples at 900 C for 1 hour followed by 3 minutes in which the sample could cool to room temperature in an ambient temperature air stream.

  6. EFTF cobalt test assembly results

    International Nuclear Information System (INIS)

    Rawlins, J.A.; Wootan, D.W.; Carter, L.L.; Brager, H.R.; Schenter, R.E.

    1988-01-01

    A cobalt test assembly containing yttrium hydride pins for neutron moderation was irradiated in the Fast Flux Test Facility during Cycle 9A for 137.7 equivalent full power days at a power level fo 291 MW. The 36 test pins consisted of a batch of 32 pins containing cobalt metal to produce Co-60, and a set of 4 pins with europium oxide to produce Gd-153, a radioisotope used in detection of the bone disease Osteoporosis. Post-irradiation examination of the cobalt pins determined the Co-60 produced with an accuracy of about 5 %. The measured Co-60 spatially distributed concentrations were within 20 % of the calculated concentrations. The assembly average Co-60 measured activity was 4 % less than the calculated value. The europium oxide pins were gamma scanned for the europium isotopes Eu-152 and Eu-154 to an absolute accuracy of about 10 %. The measured europium radioisotpe anc Gd-153 concentrations were within 20 % of calculated values. In conclusion, the hydride assembly performed well and is an excellent vehicle for many Fast Flux Test Facility isotope production applications. The results also demonstrate that the calculational methods developed by the Westinghouse Hanford Company are very accurate. (author)

  7. Investigating assumptions of crown archetypes for modelling LiDAR returns

    NARCIS (Netherlands)

    Calders, K.; Lewis, P.; Disney, M.; Verbesselt, J.; Herold, M.

    2013-01-01

    LiDAR has the potential to derive canopy structural information such as tree height and leaf area index (LAI), via models of the LiDAR signal. Such models often make assumptions regarding crown shape to simplify parameter retrieval and crown archetypes are typically assumed to contain a turbid

  8. Synthesis and characterization of an iron complex bearing a cyclic tetra-N-heterocyclic carbene ligand: An artifical heme analogue?

    KAUST Repository

    Anneser, Markus R.

    2015-04-20

    An iron(II) complex with a cyclic tetradentate ligand containing four N-heterocyclic carbenes was synthesized and characterized by means of NMR and IR spectroscopies, as well as by single-crystal X-ray structure analysis. The iron center exhibits an octahedral coordination geometry with two acetonitrile ligands in axial positions, showing structural analogies with porphyrine-ligated iron complexes. The acetonitrile ligands can readily be substituted by other ligands, for instance, dimethyl sulfoxide, carbon monoxide, and nitric oxide. Cyclic voltammetry was used to examine the electronic properties of the synthesized compounds. © 2015 American Chemical Society.

  9. N-BUTYL SUBSTITUTED N-HETEROCYCLIC CARBENE-PD(II-PYRIDINE (PEPPSI COMPLEXES: SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY IN THE SUZUKI-MIYAURA REACTION

    Directory of Open Access Journals (Sweden)

    Rukiye Fırıncı

    2016-08-01

    Full Text Available A series of N-butyl substituted imidazolium salts, (1a-c and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI themed palladium N-heterocyclic carbene complexes (2a-c were synthesized and characterized. Pd-NHC complexes were fully determined by elemental analysis and spectroscopic. The synthesized complexes were tested in Suzuki-Miyaura cross-coupling reaction. These complexes were found to be efficient catalysts for the Suzuki-Miyaura reaction of phenylboronic acid with aryl bromides.

  10. Effect of Cobalt Supplementation on Performance of growing Calves

    Directory of Open Access Journals (Sweden)

    V.Nagabhushana

    Full Text Available The experiment was conducted to study the effect of critical supplementation of wheat straw with cobalt on fibre utilization and nutrient utilization in growing cross-bred male calves. Twenty-one crossbred (HF X Local male growing calves of 3-4 months age were fed with wheat straw based diet consisting without (Co0 and with 1 (Co1 and 6 (Co6 ppm cobalt as cobaltous chloride. There was no significant difference in intake of wheat straw, concentrate and DMI between the three groups and the ratio between concentrate and wheat straw was maintained at 40:60 irrespective of dietary level of cobalt. Similarly, average cumulative body weight, net gain in body weight or feed efficiency did not differ significantly between treatments. No significant effect was observed on the digestibility of dry matter, organic matter, crude protein, ether extract and fibre constituents like NDF, ADF, hemicellulose or cellulose by supplementation of 1 and 6 ppm Co to the diet of growing calves. Balance of nutrients such as Nitrogen, Calcium and Phosphorus was similar and positive in all the treatment groups. TDN and DCP values of the experimental diets remained almost similar irrespective of dietary level of cobalt. [Veterinary World 2008; 1(10.000: 299-302

  11. Clinical examination of leucite-reinforced glass-ceramic crowns (Empress) in general practice: a retrospective study.

    Science.gov (United States)

    Sjögren, G; Lantto, R; Granberg, A; Sundström, B O; Tillberg, A

    1999-01-01

    The purpose of this study was to retrospectively evaluate leucite reinforced-glass ceramic crowns (Empress) placed in patients who regularly visit general practices. One hundred ten Empress crowns, placed in 29 patients who visited a general practice on a regular basis, were evaluated according to the California Dental Association's (CDA) quality evaluation system. In addition, the occurrence of plaque and certain gingival conditions was evaluated. All crowns were luted with resin composite cement. The mean and median years in function for the crowns were 3.6 and 3.9 years, respectively. Based on the CDA criteria, 92% of the 110 crowns were rated "satisfactory." Eighty-six percent were given the CDA rating "excellent" for margin integrity. Fracture was registered in 6% of the 110 crowns. Of the remaining 103 crowns, the CDA rating excellent was given to 74% for anatomic form, 86% for color, and 90% for surface. No significant differences (P > 0.05) were observed regarding fracture rates between anterior and posterior crowns. With regard to the occurrence of plaque and bleeding on probing, no significant differences (P > 0.05) were observed between the Empress crowns and the controls. Most of the fractured crowns had been placed on molars or premolars. Although the difference between anterior and posterior teeth was not statistically significant with respect to the fracture rates obtained, the number of fractured crowns placed on posterior teeth exceeded that of those placed on anterior teeth. The difference between the fracture rates may have clinical significance, and the risk of fracture has to be taken into consideration when placing crowns on teeth that are likely to be subjected to high stress levels.

  12. Synthesis of a 1-Aryl-2,2-chlorosilyl(phosphasilene Coordinated by an N-Heterocyclic Carbene

    Directory of Open Access Journals (Sweden)

    Andreas Wolfgang Kyri

    2016-09-01

    Full Text Available Phosphasilenes, P=Si doubly bonded compounds, have received considerable attention due to their unique physical and chemical properties. We report on the synthesis and structure of a chlorophosphasilene coordinated by an N-heterocyclic carbene (NHC, which has the potential of functionalization at the Si–Cl moiety. Treatment of a silylphosphine, ArPH–SiCl2RSi (Ar = bulky aryl group, RSi = Si(SiMe33 with two equivalents of Im-Me4 (1,3,4,5-tetramethylimidazol-2-ylidene afforded the corresponding NHC-coordinated phosphasilene, ArP=SiClRSi(Im-Me4 as a stable compound. Bonding properties of the P=Si bond coordinated to an NHC will be discussed on the basis of theoretical calculations.

  13. Modelling initial mortality of Abies religiosa in a crown fire in Mexico

    Directory of Open Access Journals (Sweden)

    Salomé Temiño-Villota

    2016-04-01

    Full Text Available Aim of study: The objectives of this work were to determine which morphological and fire severity variables may help explain the mortality of adult Abies religiosa (Kunth Schltdl. & Cham., to model the probability of this species after being affected by crown fire, and to obtain more elements to classify the sacred fir in terms of fire resistance. This type of studies are relevant to estimate the impact of crown fires on the climax forests that forms this species.Area of study: The burned forest was located in the southern Mexico City, borough.Material and methods: Morphological variables and fire severity indicators were collected for 335 Abies religiosa trees burned by a mixed severity fire. Logistic regression was used to analyze data and develop models that best explained tree mortality.Main results: Survival was 26.9%. The models for height (p≤0.0001, diameter at breast height (p=0.0082, crown length (p≤0.0001 and crown base height (p≤0.0001 were significant, with a negative relationship between each one of these variables and probability of mortality. The significant severity variables were lethal scorch height (p≤0.0001 and crown kill (p≤ 0.0001, which have a direct relationship with probability of mortality.Highlights: This species is moderately fire-resistant. Crown kill ≥ 70% markedly increases mortality. Silvicultural activities such as pruning, thinning and fuel management can reduce the risk of crown fires.

  14. Modelling initial mortality of Abies religiosa in a crown fire in Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Temiño-Villota, S.; Rodríguez-Trejo, D.A.; Molina Terrén, D.M.; Ryan, K.

    2016-07-01

    Aim of the study: The objectives of this work were to determine which morphological and fire severity variables may help explain the mortality of adult Abies religiosa (Kunth) Schltdl. & Cham., to model the probability of this species after being affected by crown fire, and to obtain more elements to classify the sacred fir in terms of fire resistance. This type of studies are relevant to estimate the impact of crown fires on the climax forests that forms this species. Area of study: The burned forest was located in the southern Mexico City, borough. Material and methods: Morphological variables and fire severity indicators were collected for 335 Abies religiosa trees burned by a mixed severity fire. Logistic regression was used to analyze data and develop models that best explained tree mortality. Main results: Survival was 26.9%. The models for height (p≤0.0001), diameter at breast height (p=0.0082), crown length (p≤0.0001) and crown base height (p≤0.0001) were significant, with a negative relationship between each one of these variables and probability of mortality. The significant severity variables were lethal scorch height (p≤0.0001) and crown kill (p≤ 0.0001), which have a direct relationship with probability of mortality. Highlights: This species is moderately fire-resistant. Crown kill ≥ 70% markedly increases mortality. Silvicultural activities such as pruning, thinning and fuel management can reduce the risk of crown fires. (Author)

  15. In situ fabrication and characterization of cobalt ferrite nanorods/graphene composites

    International Nuclear Information System (INIS)

    Fu, Min; Jiao, Qingze; Zhao, Yun

    2013-01-01

    Cobalt ferrite nanorods/graphene composites were prepared by a one-step hydrothermal process using NaHSO 3 as the reducing agent and 1-propyl-3-hexadecylimidazolium bromide as the structure growth-directing template. The reduction of graphene oxide and the in situ formation of cobalt ferrite nanorods were accomplished in a one-step reaction. The structure and morphology of as-obtained composites were characterized by field emission scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, atomic force microscope, X-ray diffractometer, Fourier transform infrared spectra, X-ray photoelectron spectroscopy and Raman spectroscopy. Uniform rod-like cobalt ferrites with diameters of about 100 nm and length of about 800 nm were homogeneously distributed on the graphene sheets. The hybrid materials showed a saturation magnetization of 42.5 emu/g and coercivity of 495.1 Oe at room temperature. The electromagnetic parameters were measured using a vector network analyzer. A minimum reflection loss (RL) of − 25.8 dB was observed at 16.1 GHz for the cobalt ferrite nanorods/graphene composites with a thickness of 2 mm, and the effective absorption frequency (RL < − 10 dB) ranged from 13.5 to 18.0 GHz. The composites exhibited better absorbing properties than the cobalt ferrite nanorods and the mixture of cobalt ferrite nanorods and graphene. - Highlights: • Reduction of GO and formation of ferrites were accomplished in a one-step reaction. • Ionic liquid was used to control 1D growth of ferrite nanorods for the first time. • Cobalt ferrite nanorods/graphene composites showed dielectric and magnetic loss. • Cobalt ferrite nanorods/graphene composites exhibited better absorbing properties

  16. Radioactive and stable cobalt concentrations in mussel in Kyushu island, Japan

    International Nuclear Information System (INIS)

    Momoshima, Noriyuki; Shiki, Atsushi; Takashima, Yoshimasa; Maki, Takao; Koriyama, Munehiro; Shimozono, Seika; Imamura, Hiroka; Nakamata, Kojiro.

    1985-01-01

    Two kinds of mussel, Septifer virgatus and Mytilus edulis, were collected from Kyushu island, Japan, in order to elucidate a background level of 60 Co, which is one of the most significant radionuclide for environmental monitoring around a nuclear power plant. The mussels were collected from 7 locations in 1983 and classified 2 or 3 groups depending on their shell size at each location. Activities of 60 Co were measured by a low-background β counter after purified by means of chemical separation and electrodeposition. Stable cobalt concentrations were determined by colorimetric method. The concentrations of cobalt in Septifer virgatus are one order higher level than that in Mytilus edulis. There are not so large difference in cobalt content depending on shell size so long as comparing them at the same location. The radioactivities in mussels show the same trend as stable cobalt. It has become apparent that Septifer virgatus has a tendency to concentrate cobalt with growing but Mytilus edulis is opposite. The cobalt-60 introduced to sea from nuclear explosions seems to be relatively constant in coastal seawater since specific activities are distributed in a narrow range in spite of kind, shell size and location. (author)

  17. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard

    2013-01-01

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.

    2013-09-18

    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  20. Smoothing an isolated interface of cobalt-copper under irradiation by low-energy argon ions

    International Nuclear Information System (INIS)

    Stognij, A.I.; Novitskij, N.N.; Stukalov, O.M.

    2003-01-01

    Multilayer film structures, i.e. gold layer-copper-cobalt, are considered. It is shown that the structure, where cobalt surface prior to copper layer deposition was subjected to additional irradiation by a flow of argon ions, features the smoothest surface. The conclusion is made about smoothing out of cobalt-copper interface as a result of multiple collisions of argon slow ions and cobalt atoms during braking within two or three upper atomic rows of the cobalt layer [ru

  1. Preliminary studies of cobalt complexation in groundwater

    International Nuclear Information System (INIS)

    Warwick, P.; Shaw, P.; Williams, G.M.; Hooker, P.J.

    1988-01-01

    A relatively non-invasive method has been used to separate complexed from free cobalt-60 in groundwater, using the weak cationic adsorption properties of Sephadex gels, and a mobile phase of natural groundwater. Results show the kinetics of Co complex formation in groundwater to be slow, and that the equilibrium position is affected by temperature, cobalt concentration and the ionic/organic strength of the groundwater. The addition of DAEA cellulose to the groundwater to remove humic material, also removed the majority of organic species which absorb UV at 254 nm, but 45% of the original total organic carbon remained, and the amount of complexed cobalt left in solution was only reduced to 76% of its former concentration. This suggests that the completed Co species separated by the method described in this paper are a mixture of inorganic and organic compounds, and studies are therefore continuing to establish their exact nature. (author)

  2. Preliminary studies of cobalt complexation in groundwater

    International Nuclear Information System (INIS)

    Warwick, P.; Shaw, P.; Williams, G.M.; Hooker, P.J.

    1988-01-01

    A relatively non-invasive method has been used to separate complexed from free cobalt-60 in groundwater, using the weak cationic adsorption properties of Sephadex gels, and a mobile phase of natural groundwater. Results show the kinetics of Co complex formation in groundwater to be slow, and that the equilibrium position is affected by temperature, cobalt concentration and the ionic/organic strength of the groundwater. The addition of DEAE cellulose to the groundwater to remove humic material, also removed the majority of organic species with absorb UV at 254 nm, but 45% of the original total organic carbon remained, and the amount of complexed cobalt left in solution was only reduced to 76% of its former concentration. This suggests that the complexed Co species separated by the method described in this paper are a mixture of inorganic and organic compounds, and studies are therefore continuing to establish their exact nature. (orig.)

  3. Cobalt dinitrosoalkane complexes in the C-H functionalization of olefins.

    Science.gov (United States)

    Schomaker, Jennifer M; Boyd, W Christopher; Stewart, Ian C; Toste, F Dean; Bergman, Robert G

    2008-03-26

    The use of cobalt dinitrosoalkane complexes in the C-H functionalization of alkenes has been demonstrated. Reaction of a series of alkenes with Me4CpCo(CO)2 in the presence of NO generates intermediate cobalt dinitrosoalkane complexes that can be deprotonated alpha to the nitrosyl group and added to various Michael acceptors. The resultant products can then undergo retrocycloaddition reactions in the presence of the original alkene to regenerate the starting cobalt dinitrosoalkane complex and release the functionalized alkene.

  4. Li-ion battery recycling and cobalt flow analysis in Japan

    OpenAIRE

    Asari, Misuzu; Sakai, Shin-ichi

    2013-01-01

    Batteries sometimes contain precious or toxic substances (e.g. nickel, cobalt, lead, mercury, cadmium). However, the collection and recycling rate of small batteries were low in Japan. We focus on cobalt in lithium ion (Li-ion) batteries and conduct chemical analysis, questioner survey and flow analysis in Japan.Results of chemical analysis showed that the concentration of cobalt in Li-ion batteries was around 20% regardless of the year manufactured or the manufacturer. As a result of the con...

  5. Cobalt uptake and binding in human red blood cells

    DEFF Research Database (Denmark)

    Simonsen, Lars Ole; Brown, Anthony M; Harbak, Henrik

    2011-01-01

    of cobalt, and also from the initial slope of the cobalt buffering curve. The cobalt accumulation is similar in fed and ATP-depleted cells. The buffering curve for [Co(T)](c) can be fitted by a Michaelis type function with B(max)=24 mmol (l cells)(-1) and half-saturation at 240 µM [Co(2+)](c). The tracer...... reversibly bound, being releasable by excess extracellular EGTA in the presence of A23187, and partly tightly bound, remaining in the cells even at high ionophore concentrations. The tightly bound fraction builds up over time, and is larger and develops earlier in fed cells compared to ATP-depleted cells......-migrate with hemoglobin in Sephadex column chromatography of a lysate of (57)Co-loaded cells. (57)Co also co-migrates with hemoglobin when added to a lysate of unlabeled cells or to a solution of purified hemoglobin, in both cases with a time-dependent development of tight binding. Cobalt is known to bind to the globin...

  6. Treatment Recommendations for Single-Unit Crowns: Findings from The National Dental Practice-Based Research Network

    Science.gov (United States)

    McCracken, Michael S.; Louis, David R.; Litaker, Mark S.; Minyé, Helena M.; Mungia, Rahma; Gordan, Valeria V.; Marshall, Don G.; Gilbert, Gregg H.

    2016-01-01

    Background Objectives were to: (1) quantify practitioner variation in likelihood to recommend a crown; and (2) test whether certain dentist, practice, and clinical factors are significantly associated with this likelihood. Methods Dentists in the National Dental Practice-Based Research Network completed a questionnaire about indications for single-unit crowns. In four clinical scenarios, practitioners ranked their likelihood of recommending a single-unit crown. These responses were used to calculate a dentist-specific “Crown Factor” (CF; range 0–12). A higher score implies a higher likelihood to recommend a crown. Certain characteristics were tested for statistically significant associations with the CF. Results 1,777 of 2,132 eligible dentists responded (83%). Practitioners were most likely to recommend crowns for teeth that were fractured, cracked, endodontically-treated, or had a broken restoration. Practitioners overwhelmingly recommended crowns for posterior teeth treated endodontically (94%). Practice owners, Southwest practitioners, and practitioners with a balanced work load were more likely to recommend crowns, as were practitioners who use optical scanners for digital impressions. Conclusions There is substantial variation in the likelihood of recommending a crown. While consensus exists in some areas (posterior endodontic treatment), variation dominates in others (size of an existing restoration). Recommendations varied by type of practice, network region, practice busyness, patient insurance status, and use of optical scanners. Practical Implications Recommendations for crowns may be influenced by factors unrelated to tooth and patient variables. A concern for tooth fracture -- whether from endodontic treatment, fractured teeth, or large restorations -- prompted many clinicians to recommend crowns. PMID:27492046

  7. Stress and Reliability Analysis of a Metal-Ceramic Dental Crown

    Science.gov (United States)

    Anusavice, Kenneth J; Sokolowski, Todd M.; Hojjatie, Barry; Nemeth, Noel N.

    1996-01-01

    Interaction of mechanical and thermal stresses with the flaws and microcracks within the ceramic region of metal-ceramic dental crowns can result in catastrophic or delayed failure of these restorations. The objective of this study was to determine the combined influence of induced functional stresses and pre-existing flaws and microcracks on the time-dependent probability of failure of a metal-ceramic molar crown. A three-dimensional finite element model of a porcelain fused-to-metal (PFM) molar crown was developed using the ANSYS finite element program. The crown consisted of a body porcelain, opaque porcelain, and a metal substrate. The model had a 300 Newton load applied perpendicular to one cusp, a load of 30ON applied at 30 degrees from the perpendicular load case, directed toward the center, and a 600 Newton vertical load. Ceramic specimens were subjected to a biaxial flexure test and the load-to-failure of each specimen was measured. The results of the finite element stress analysis and the flexure tests were incorporated in the NASA developed CARES/LIFE program to determine the Weibull and fatigue parameters and time-dependent fracture reliability of the PFM crown. CARES/LIFE calculates the time-dependent reliability of monolithic ceramic components subjected to thermomechanical and/Or proof test loading. This program is an extension of the CARES (Ceramics Analysis and Reliability Evaluation of Structures) computer program.

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

    KAUST Repository

    Marston, J. O.

    2016-04-05

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

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

    Science.gov (United States)

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

    2007-04-01

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

  10. An in-vitro investigation of the accuracy of fit of Procera and Empress crowns.

    Science.gov (United States)

    Fleming, Garry J R; Dobinson, Marie M; Landini, Gabriel; Harris, Jonathan J

    2005-09-01

    The current study aimed to investigate the accuracy of fit and the reproducibility of inner crown profile for two types of high strength ceramics, IPS Empress and Procera. Procera and Empress crowns with four different morphologies were cemented to dies using zinc phosphate dental cement. Vertical and horizontal sections were made through each of the crown/die preparations and images of the vertical sections were compared for curvature reproduction by alignment using image processing. Measurements were made on horizontal sections to determine cement layer thickness. Alignment of the crowns using image analysis identified quantifiable variations in the inner surface profile compared with the outer surface of the die. The largest differences occurred from the cusp tips to the occlusal adaptation area and differences in surface profile were less pronounced for Procera than Empress crowns. Marginal gap varied independently of ceramic or internal crown shape from 7-529 microm for Procera and 26-548 microm for Empress. IPS Empress has a superior ability to reproduce the inner surface profile of the crown morphologies investigated compared with Procera. The reduced reproduction of surface profile was associated with an increased cement thickness at the occlusal contact area that may inadvertently lead to failure of the crowns functional characteristics.

  11. The aesthetic treatment for anterior teeth with lost crown by endorestoration

    Directory of Open Access Journals (Sweden)

    Nanik Zubaidah

    2009-06-01

    Full Text Available Background: The aesthetic has an important role in social life, especially the anterior teeth. The aesthetic abnormality of anterior teeth i.e. discoloration, malpotition or the anterior teeth with crown damage for more than one third or all part of crown is lost due to caries or other causes, will influence its appearance especially during smile. Purpose: The aim of this case report, therefore, is to show how teeth with clinical crown lost or only the root left still can be treated by endorestoration treatment in order to reconstruct the shape and function of the teeth similar to the original ones. Case: Female 52 years old with the lost crown of anterior teeth. The patient did not want her teeth to be extracted. Case Management: The abnormality of these teeth are still able to be reconstructed by endorestoration i.e. endodontic treatment with post and core insertion in the root canal will increase its retention and recovery by the porcelain crown fused to metal to recover the original formation and aesthetic and thus has the normal refunction. The treatment, it improve the confidence of the patient, and also can function normally. The patient did not feel pain. Ronsenography showed the periapical lesion diminished, the neighbor gingival was going better in both function and color. Conclusion: Endorestoration treatment on the anterior teeth with lost crown could recover the normal function, dental aesthetic and self confidence.

  12. Self-subunit swapping occurs in another gene type of cobalt nitrile hydratase.

    Directory of Open Access Journals (Sweden)

    Yi Liu

    Full Text Available Self-subunit swapping is one of the post-translational maturation of the cobalt-containing nitrile hydratase (Co-NHase family of enzymes. All of these NHases possess a gene organization of , which allows the activator protein to easily form a mediatory complex with the α-subunit of the NHase after translation. Here, we discovered that the incorporation of cobalt into another type of Co-NHase, with a gene organization of , was also dependent on self-subunit swapping. We successfully isolated a recombinant NHase activator protein (P14K of Pseudomonas putida NRRL-18668 by adding a Strep-tag N-terminal to the P14K gene. P14K was found to form a complex [α(StrepP14K(2] with the α-subunit of the NHase. The incorporation of cobalt into the NHase of P. putida was confirmed to be dependent on the α-subunit substitution between the cobalt-containing α(StrepP14K(2 and the cobalt-free NHase. Cobalt was inserted into cobalt-free α(StrepP14K(2 but not into cobalt-free NHase, suggesting that P14K functions not only as a self-subunit swapping chaperone but also as a metallochaperone. In addition, NHase from P. putida was also expressed by a mutant gene that was designed with a order. Our findings expand the general features of self-subunit swapping maturation.

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

    Directory of Open Access Journals (Sweden)

    Jochen Gohlke

    Full Text Available Crown gall tumors develop after integration of the T-DNA of virulent Agrobacterium tumefaciens strains into the plant genome. Expression of the T-DNA-encoded oncogenes triggers proliferation and differentiation of transformed plant cells. Crown gall development is known to be accompanied by global changes in transcription, metabolite levels, and physiological processes. High levels of abscisic acid (ABA in crown galls regulate expression of drought stress responsive genes and mediate drought stress acclimation, which is essential for wild-type-like tumor growth. An impact of epigenetic processes such as DNA methylation on crown gall development has been suggested; however, it has not yet been investigated comprehensively. In this study, the methylation pattern of Arabidopsis thaliana crown galls was analyzed on a genome-wide scale as well as at the single gene level. Bisulfite sequencing analysis revealed that the oncogenes Ipt, IaaH, and IaaM were unmethylated in crown galls. Nevertheless, the oncogenes were susceptible to siRNA-mediated methylation, which inhibited their expression and subsequently crown gall growth. Genome arrays, hybridized with methylated DNA obtained by immunoprecipitation, revealed a globally hypermethylated crown gall genome, while promoters were rather hypomethylated. Mutants with reduced non-CG methylation developed larger tumors than the wild-type controls, indicating that hypermethylation inhibits plant tumor growth. The differential methylation pattern of crown galls and the stem tissue from which they originate correlated with transcriptional changes. Genes known to be transcriptionally inhibited by ABA and methylated in crown galls became promoter methylated upon treatment of A. thaliana with ABA. This suggests that the high ABA levels in crown galls may mediate DNA methylation and regulate expression of genes involved in drought stress protection. In summary, our studies provide evidence that epigenetic processes

  14. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst

    Directory of Open Access Journals (Sweden)

    Dewi Tristantini

    2016-03-01

    Received: 10th November 2015; Revised: 10th February 2016; Accepted: 16th February 2016 How to Cite: Tristantini, D., Suwignjo, R.K. (2016. Lump Kinetic Analysis of Syngas Composition Effect on Fischer-Tropsch Synthesis over Cobalt and Cobalt-Rhenium Alumina Supported Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 84-92. (doi:10.9767/bcrec.11.1.424.84-92 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.424.84-92

  15. Tailoring the magnetic properties of cobalt-ferrite nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Vega, A. Estrada de la; Garza-Navarro, M. A., E-mail: marco.garzanr@uanl.edu.mx; Durán-Guerrero, J. G.; Moreno Cortez, I. E.; Lucio-Porto, R.; González-González, V. [Universidad Autónoma de Nuevo León, Facultad de Ingeniería Mecánica y Eléctrica (Mexico)

    2016-01-15

    In this contribution, we report on the tuning of magnetic properties of cobalt-ferrite nanoclusters. The cobalt-ferrite nanoclusters were synthesized from a two-step approach that consists of the synthesis of cobalt-ferrite nanoparticles in organic media, followed by their dispersion into aqueous dissolution to form an oil-in-water emulsion. These emulsions were prepared at three different concentrations of the cationic surfactant cetyltrimethylammonium bromide (CTAB), in order to control the size and clustering density of the nanoparticles in the nanoclusters. The synthesized samples were characterized by transmission electron microscopy and their related techniques, such as bright-field and Z-contrast imaging, electron diffraction and energy-dispersive X-ray spectrometry; as well as static magnetic measures. The experimental evidence indicates that the size, morphology, and nanoparticles clustering density in the nanoclusters is highly dependent of the cobalt-ferrite:CTAB molar ratio that is used in their synthesis. In addition, due to the clustering of the nanoparticles into the nanoclusters, their magnetic moments are blocked to relax cooperatively. Hence, the magnetic response of the nanoclusters can be tailored by controlling the size and nanoparticles clustering density.

  16. A semi-empirical model for predicting crown diameter of cedrela ...

    African Journals Online (AJOL)

    A semi-empirical model relating age and breast height has been developed to predict individual tree crown diameter for Cedrela odorata (L) plantation in the moist evergreen forest zones of Ghana. The model was based on field records of 269 trees, and could determine the crown cover dynamics, forecast time of canopy ...

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

    African Journals Online (AJOL)

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

  18. Nanotoxicity of cobalt induced by oxidant generation and glutathione depletion in MCF-7 cells.

    Science.gov (United States)

    Akhtar, Mohd Javed; Ahamed, Maqusood; Alhadlaq, Hisham A; Alshamsan, Aws

    2017-04-01

    There are very few studies regarding the biological activity of cobalt-based nanoparticles (NPs) and, therefore, the possible mechanism behind the biological response of cobalt NPs has not been fully explored. The present study was designed to explore the potential mechanisms of the cytotoxicity of cobalt NPs in human breast cancer (MCF-7) cells. The shape and size of cobalt NPs were characterized by scanning and transmission electron microscopy (SEM and TEM). The crystallinity of NPs was determined by X-ray diffraction (XRD). The dissolution of NPs was measured in phosphate-buffered saline (PBS) and culture media by atomic absorption spectroscopy (AAS). Cytotoxicity parameters, such as [3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyl tetrazolium bromide] (MTT), neutral red uptake (NRU), and lactate dehydrogenase (LDH) release suggested that cobalt NPs were toxic to MCF-7 cells in a dose-dependent manner (50-200μg/ml). Cobalt NPs also significantly induced reactive oxygen species (ROS) generation, lipid peroxidation (LPO), mitochondrial outer membrane potential loss (MOMP), and activity of caspase-3 enzymes in MCF-7 cells. Moreover, cobalt NPs decreased intracellular antioxidant glutathione (GSH) molecules. The exogenous supply of antioxidant N-acetyl cysteine in cobalt NP-treated cells restored the cellular GSH level and prevented cytotoxicity that was also confirmed by microscopy. Similarly, the addition of buthionine-[S, R]-sulfoximine, which interferes with GSH biosynthesis, potentiated cobalt NP-mediated toxicity. Our data suggested that low solubility cobalt NPs could exert toxicity in MCF-7 cells mainly through cobalt NP dissolution to Co 2+ . Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    DEFF Research Database (Denmark)

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

    2003-01-01

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

  20. [Effects of repeated firing on microleakage of selective laser melting ceramic crowns].

    Science.gov (United States)

    Zhong, Qun; Peng, Yan; Wu, Xue-Ying; Weng, Jia-Wei

    2016-12-01

    To investigate the effects of repeated firing on microleakage of selective laser melting ceramic crowns. Fifty molars were randomly divided into 2 groups (25 teeth in each group). Teeth in group A received a chamfer finish line preparation, whereas teeth in group B received a shoulder finish line. After SLM metal crowns were fabricated, all the crowns received initial oxidation step, opaque firing, dentin firing and glaze firing, then crowns in each group were randomly divided into 5 sub-groups according to different time of clinical firings. Glass ionomer was applied for bonding. After 5000 thermocycles ranging from 5degrees centigrade to 55degrees centigrade, all the specimens was evaluated by dye penetration and then microleakage was examined under light microscopy. The data were analyzed with SPSS 20.0 software package. Microleakage between all specimens of group A were not statistically significant (P>0.05) whereas that of group B were statistically significant (P<0.05); After the fifth time of clinical firing, microleakage of specimens in group B(B5) were significantly higher than that of group A(A5). Repeated firings had no significant influence on marginal microleakage of SLM ceramic crowns whereas the crowns of chamfer finish lines result in better clinical performance after repeated firings.

  1. Adsorption, Bioaccumulation and Kinetics Parameters of the Phytoremediation of Cobalt from Wastewater Using Elodea canadensis.

    Science.gov (United States)

    Mosoarca, Giannin; Vancea, Cosmin; Popa, Simona; Boran, Sorina

    2018-05-01

    Present paper investigates the phytoremediation of cobalt from wastewaters using Elodea canadensis. Bioaccumulation tests were conducted at various concentrations of cobalt ranging from 1 to 15 mg/L. Final concentrations of cobalt in wastewaters, after phytoremediation, were less than 1 mg/L. E. canadensis' hyperaccumulator character with regard to cobalt is emphasised by the amount of cobalt retained: 0.39% ± 0.02% of dry mass at an initial concentration in wastewater of 15 mg/L. After 14 days of exposure to contaminant, the biomass as well as the relative growth rate has increased with the amount of cobalt in wastewaters, the plant manifesting an excellent tolerance to cobalt exposure. Adsorption of cobalt ions by E. canadensis can be well described by the Langmuir adsorption isotherm and the pseudo-second-order model equation.

  2. Activation of cobalt 60 in the LVR-15 reactor core

    International Nuclear Information System (INIS)

    Melichar, F.

    1995-12-01

    Cobalt disks were irradiated in the LVR-15 reactor and the relevant cobalt-60 production parameters, particularly the formation rate, were measured. The data were compared with those from previous work by other authors and some discrepancies were found. It is concluded that additional experiments have to be performed in order to obtain reliable data, usable in economic balance assessment with respect to the use of hot chambers for the production of sealed cobalt-60 sources. (P.A.). 4 tabs., 3 refs., 10 annexes

  3. Half-sandwich cobalt complexes in the metal-organic chemical vapor deposition process

    Energy Technology Data Exchange (ETDEWEB)

    Georgi, Colin [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Hapke, Marko; Thiel, Indre [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), Albert-Einstein-Straße 29a, Rostock 18059 (Germany); Hildebrandt, Alexander [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany); Waechtler, Thomas; Schulz, Stefan E. [Fraunhofer Institute of Electronic Nano Systems (ENAS), Technologie-Campus 3, Chemnitz 09126 (Germany); Technische Universität Chemnitz, Center for Microtechnologies (ZfM), Chemnitz 09107 (Germany); Lang, Heinrich, E-mail: heinrich.lang@chemie.tu-chemnitz.de [Technische Universität Chemnitz, Faculty of Natural Science, Institute of Chemistry, Inorganic Chemistry, Chemnitz 09107 (Germany)

    2015-03-02

    A series of cobalt half-sandwich complexes of type [Co(η{sup 5}-C{sub 5}H{sub 5})(L)(L′)] (1: L, L′ = 1,5-hexadiene; 2: L = P(OEt){sub 3}, L′ = H{sub 2}C=CHSiMe{sub 3}; 3: L = L′ = P(OEt){sub 3}) has been studied regarding their physical properties such as the vapor pressure, decomposition temperature and applicability within the metal-organic chemical vapor deposition (MOCVD) process, with a focus of the influence of the phosphite ligands. It could be shown that an increasing number of P(OEt){sub 3} ligands increases the vapor pressure and thermal stability of the respective organometallic compound. Complex 3 appeared to be a promising MOCVD precursor with a high vapor pressure and hence was deposited onto Si/SiO{sub 2} (100 nm) substrates. The resulting reflective layer is closed, dense and homogeneous, with a slightly granulated surface morphology. X-ray photoelectron spectroscopy (XPS) studies demonstrated the formation of metallic cobalt, cobalt phosphate, cobalt oxide and cobalt carbide. - Highlights: • Thermal studies and vapor pressure measurements of cobalt half-sandwich complexes was carried out. • Chemical vapor deposition with cobalt half-sandwich complexes is reported. • The use of Co-phosphites results in significant phosphorous-doped metallic layers.

  4. Nickel and cobalt release from jewellery and metal clothing items in Korea.

    Science.gov (United States)

    Cheong, Seung Hyun; Choi, You Won; Choi, Hae Young; Byun, Ji Yeon

    2014-01-01

    In Korea, the prevalence of nickel allergy has shown a sharply increasing trend. Cobalt contact allergy is often associated with concomitant reactions to nickel, and is more common in Korea than in western countries. The aim of the present study was to investigate the prevalence of items that release nickel and cobalt on the Korean market. A total of 471 items that included 193 branded jewellery, 202 non-branded jewellery and 76 metal clothing items were sampled and studied with a dimethylglyoxime (DMG) test and a cobalt spot test to detect nickel and cobalt release, respectively. Nickel release was detected in 47.8% of the tested items. The positive rates in the DMG test were 12.4% for the branded jewellery, 70.8% for the non-branded jewellery, and 76.3% for the metal clothing items. Cobalt release was found in 6.2% of items. Among the types of jewellery, belts and hair pins showed higher positive rates in both the DMG test and the cobalt spot test. Our study shows that the prevalence of items that release nickel or cobalt among jewellery and metal clothing items is high in Korea. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  5. Rhodium-catalyzed NH insertion of pyridyl carbenes derived from pyridotriazoles: a general and efficient approach to 2-picolylamines and imidazo[1,5-a]pyridines.

    Science.gov (United States)

    Shi, Yi; Gulevich, Anton V; Gevorgyan, Vladimir

    2014-12-15

    A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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...

  7. 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...

  8. [An in vitro study of the fracture strength of tooth preparations for Empress 2 veneers and crowns and mandibular incisors restored with Empress 2 veneers and crowns].

    Science.gov (United States)

    Wei, Xue; Li, Yan

    2009-12-01

    To compare the fracture resistance of mandibular incisors' preparations for veneers and crowns, mandibular incisors restored with Empress 2 veneers and crowns. 50 human mandibular incisors were randomly divided into five groups. Each group consisted of ten teeth and the treatment obtained as follows: A, tooth preparations for veneers; B, tooth preparations for crowns; C, teeth restored with veneers; D, teeth restored with crowns; E, untreated group. The teeth received standardized preparation and the restorations were manufactured with Empress 2 system and cemented with resin luting agent. The fracture resistances of teeth were measured by Instron universal testing machine and statistically analyzed with one-way ANOVA. The fracture resistances of A, B, C, D, E were (576.11 +/- 91.53), (204.13 +/- 85.88), (451.50 +/- 116.81), (386.16 +/- 117.75) and (566.05 +/- 121.37) N, respectively. The statistical analysis demonstrated significant differences between five groups. There were no significant differences between group A and E, group C and D. Tooth preparations for veneers did not significantly reduce the fracture resistance of mandibular incisor. The fracture resistance of teeth restored with Empress 2 veneers and crowns did not significantly differ from each other.

  9. World production and possible recovery of cobalt from the Kupferschiefer stratiform copper ore

    Directory of Open Access Journals (Sweden)

    Pazik Paulina M.

    2016-01-01

    Full Text Available Cobalt is recognized as a strategic metal and also E-tech element, which is crucial for worlds development. An increasing demand for cobalt forces for searching of new resources that could be explored in European countries. There are many examples of cobalt recoveries, mostly from laterite and sulphide deposits. However, the accurate choice of the technology depends on many factors. The Kupferschiefer stratiform copper ore located in Poland is the biggest deposit of cobalt in Europe. Although KGHM Polska Miedz S.A. recovers many precious metals from this ore, cobalt is not recovered yet. This metal occurs as an accompanying element, mostly in the form of cobaltite (CaAsS, with the average content of 50–80 g/Mg. In this paper a possible recovery of cobalt from the Kupferschiefer ore, with the use of hydrometallurgical methods, was investigated.

  10. Importance of cobalt for individual trophic groups in an anaerobic methanol-degrading consortium.

    OpenAIRE

    Florencio, L; Field, J A; Lettinga, G

    1994-01-01

    Methanol is an important anaerobic substrate in industrial wastewater treatment and the natural environment. Previous studies indicate that cobalt greatly stimulates methane formation during anaerobic treatment of methanolic wastewaters. To evaluate the effect of cobalt in a mixed culture, a sludge with low background levels of cobalt was cultivated in an upflow anaerobic sludge blanket reactor. Specific inhibitors in batch assays were then utilized to study the effect of cobalt on the growth...

  11. CROWN-LEVEL TREE SPECIES CLASSIFICATION USING INTEGRATED AIRBORNE HYPERSPECTRAL AND LIDAR REMOTE SENSING DATA

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2018-05-01

    Full Text Available Mapping tree species is essential for sustainable planning as well as to improve our understanding of the role of different trees as different ecological service. However, crown-level tree species automatic classification is a challenging task due to the spectral similarity among diversified tree species, fine-scale spatial variation, shadow, and underlying objects within a crown. Advanced remote sensing data such as airborne Light Detection and Ranging (LiDAR and hyperspectral imagery offer a great potential opportunity to derive crown spectral, structure and canopy physiological information at the individual crown scale, which can be useful for mapping tree species. In this paper, an innovative approach was developed for tree species classification at the crown level. The method utilized LiDAR data for individual tree crown delineation and morphological structure extraction, and Compact Airborne Spectrographic Imager (CASI hyperspectral imagery for pure crown-scale spectral extraction. Specifically, four steps were include: 1 A weighted mean filtering method was developed to improve the accuracy of the smoothed Canopy Height Model (CHM derived from LiDAR data; 2 The marker-controlled watershed segmentation algorithm was, therefore, also employed to delineate the tree-level canopy from the CHM image in this study, and then individual tree height and tree crown were calculated according to the delineated crown; 3 Spectral features within 3 × 3 neighborhood regions centered on the treetops detected by the treetop detection algorithm were derived from the spectrally normalized CASI imagery; 4 The shape characteristics related to their crown diameters and heights were established, and different crown-level tree species were classified using the combination of spectral and shape characteristics. Analysis of results suggests that the developed classification strategy in this paper (OA = 85.12 %, Kc = 0.90 performed better than Li

  12. hermo-Physical and Mechanical Properties of Unsaturated Polyester /Cobalt Ferrite Composites

    Directory of Open Access Journals (Sweden)

    Lamees Salam Faiq

    2017-04-01

    Full Text Available Unsaturated polyester was used as a matrix which was filled with different percentages of cobalt ferrite using hand lay-up method. Cobalt ferrite was synthesized using solid state ceramic method with reagent of CoO and Fe2O3. Mechanical properties such tensile strength, Young's modulus and shore D hardness of the composite have been studied. All these properties have increased by 10% with increasing cobalt ferrite contents. Also the thermal properties such thermal conductivity and specific heat capacity are highly increased as the ferrite content increased, while the thermal diffusivity increased by 22 %. On the other hand dielectric strength of composite has been measured which increased by 50% by increasing the cobalt ferrite content.

  13. Comparative evaluation of marginal leakage of provisional crowns cemented with different temporary luting cements: In vitro study.

    Science.gov (United States)

    Arora, Sheen Juneja; Arora, Aman; Upadhyaya, Viram; Jain, Shilpi

    2016-01-01

    As, the longevity of provisional restorations is related to, a perfect adaptation and a strong, long-term union between restoration and teeth structures, therefore, evaluation of marginal leakage of provisional restorative materials luted with cements using the standardized procedures is essential. To compare the marginal leakage of the provisional crowns fabricated from Autopolymerizing acrylic resin crowns and bisphenol A-glycidyl dimethacrylate (BIS-GMA) resin crowns. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin crowns and BIS-GMA resin crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin (SC-10) crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from BIS-GMA resin crowns (Protemp 4) cemented with different temporary luting cements. Freshly extracted 60 maxillary premolars of approximately similar dimensions were mounted in dental plaster. Tooth reduction with shoulder margin was planned to use a customized handpiece-holding jig. Provisional crowns were prepared using the wax pattern fabricated from computer aided designing/computer aided manufacturing milling machine following the tooth preparation. Sixty provisional crowns were made, thirty each of SC-10 and Protemp 4 and were then cemented with three different luting cements. Specimens were thermocycled, submerged in a 2% methylene blue solution, then sectioned and observed under a stereomicroscope for the evaluation of marginal microleakage. A five-level scale was used to score dye penetration in the tooth/cement interface and the results of this study was analyzed using the Chi-square test, Mann-Whitney U-test, Kruskal-Wallis H-test and the results were statistically significant P provisional crowns cemented with three different luting cements along the axial walls of

  14. Contact dermatitis to cobalt chloride with an unusual mechanism.

    Science.gov (United States)

    Arslan, Sevket; Aksan, Serkan; Ucar, Ramazan; Caliskaner, Ahmet Zafer

    2015-10-01

    Contact dermatitis is a frequent inflammatory skin disease. A suspected diagnosis is based on clinical symptoms, a plausible contact to allergens and a suitable history of dermatitis. Therefore, careful diagnosis by patch testing is of great importance because the patch testing is important to find out which allergen/material causes the complaints. Metallic allergens such as cobalt are among the most common causes of allergic contact dermatitis, but frequencies of contact dermatitis to these allergens may vary in different skin areas. Here, we report an unusual case of cobalt allergy on the skin contact with the prosthetic leg of a 30-year-old female patient. The patient developed maculopapular and vesicular lesions on her contact region of residual limb to prosthetic leg. She underwent standard patch testing, which resulted in a strong positive reaction to cobalt chloride. This case report may serve to remind doctors to be aware of potential allergic reactions to prostheses and to enable them to recognize a metal allergy if it appears. Prosthetists should also be reminded of potential allergic reactions. Cobalt can be used as an accelerator in making a prosthetic socket. Several cases have been reported concerning allergies to components of the prosthetic socket. This is the first report of sensitization to cobalt which is used in making a prosthetic leg. © The International Society for Prosthetics and Orthotics 2014.

  15. Cobalt toxicity: Chemical and radiological combined effects on HaCaT keratinocyte cell line

    International Nuclear Information System (INIS)

    Sandre, C.; Moulin, C.; Bresson, C.; Gault, N.; Poncy, J. L.; Lefaix, J. L.

    2010-01-01

    Cobalt (Co) is an essential trace element well known as a constituent of vitamin B 12 , but different compounds of Co are also described as highly toxic and/or radio-toxic for individuals or the environment. In nuclear power plants, 58 Co and 60 Co are radioactive isotopes of cobalt present as activation products of stable Co and Ni used in alloys. Skin exposure is a current occupational risk in the hard metal and nuclear industries. As biochemical and molecular cobalt-induced toxicological mechanisms are not fully identified, we investigated cobalt toxicity in a model human keratinocyte cell line, HaCaT. In this study, we propose a model to determine the in vitro chemical impact on cell viability of a soluble form of cobalt (CoCl 2 ) with or without gamma-ray doses to mimic contamination by 60 Co, to elucidate the mechanisms of cobalt intracellular chemical and radiological toxicity. Intracellular cobalt concentration was determined after HaCaT cell contamination and chemical toxicity was evaluated in terms of cellular viability and clonogenic survival. We investigated damage to DNA in HaCaT cells by combined treatment with chemical cobalt and a moderate gamma-ray dose. Additive effects of cobalt and irradiation were demonstrated. The underlying mechanism of cobalt toxicity is not clearly established, but our results seem to indicate that the toxicity of Co(II) and of irradiation arises from production of reactive oxygen species. (authors)

  16. Cobalt toxicity: Chemical and radiological combined effects on HaCaT keratinocyte cell line

    Energy Technology Data Exchange (ETDEWEB)

    Gault, N. [CEA Fontenay aux Roses, DSV/IRCM/SCSR/LRTS, 92265 Fontenay aux Rose (France); Sandre, C.; Moulin, B.; Bresson, C. [CEA, DEN, SECR, Laboratoire de Speciation des Radionucleides et des Molecules, F-91191 Gif-sur-Yvette (France); Poncy, J.L. [CEA Bruyeres Le Chatel, DSV/IRCM/SREIT/LRT, 91680 Bruyeres Le Chatel (France); Lefaix, J.L. [CEA Caen, DSV/IRCM/SRO/LARIA, 14070 Caen (France)

    2010-07-01

    Cobalt (Co) is an essential trace element well known as a constituent of vitamin B12, but different compounds of Co are also described as highly toxic and/or radio-toxic for individuals or the environment. In nuclear power plants, {sup 58}Co and {sup 60}Co are radioactive isotopes of cobalt present as activation products of stable Co and Ni used in alloys. Skin exposure is a current occupational risk in the hard metal and nuclear industries. As biochemical and molecular cobalt-induced toxicological mechanisms are not fully identified, we investigated cobalt toxicity in a model human keratinocyte cell line, HaCaT. In this study, we propose a model to determine the in vitro chemical impact on cell viability of a soluble form of cobalt (CoCl{sub 2}) with or without {gamma}-ray doses to mimic contamination by {sup 60}Co, to elucidate the mechanisms of cobalt intracellular chemical and radiological toxicity. Intracellular cobalt concentration was determined after HaCaT cell contamination and chemical toxicity was evaluated in terms of cellular viability and clonogenic survival. We investigated damage to DNA in HaCaT cells by combined treatment with chemical cobalt and a moderate {gamma}-ray dose. Additive effects of cobalt and irradiation were demonstrated. The underlying mechanism of cobalt toxicity is not clearly established, but our results seem to indicate that the toxicity of Co(II) and of irradiation arises from production of reactive oxygen species. (authors)

  17. Cobalt toxicity: Chemical and radiological combined effects on HaCaT keratinocyte cell line

    Energy Technology Data Exchange (ETDEWEB)

    Sandre, C.; Moulin, C.; Bresson, C. [CEA Saclay, DEN, SECR, Lab Speciat Radionucleides and Mol, F-91191 Gif Sur Yvette (France); Gault, N. [CEA Fontenay Roses, DSV IRCM SCSR LRTS, F-92265 Fontenay Aux Roses (France); Poncy, J. L. [CEA Bruyeres Le Chatel, DSV IRCM SREIT LRT, F-91680 Bruyeres Le Chatel (France); Lefaix, J. L. [CEA Caen, DSV IRCM SRO LARIA, F-14070 Caen (France)

    2010-07-01

    Cobalt (Co) is an essential trace element well known as a constituent of vitamin B{sub 12}, but different compounds of Co are also described as highly toxic and/or radio-toxic for individuals or the environment. In nuclear power plants, {sup 58}Co and {sup 60}Co are radioactive isotopes of cobalt present as activation products of stable Co and Ni used in alloys. Skin exposure is a current occupational risk in the hard metal and nuclear industries. As biochemical and molecular cobalt-induced toxicological mechanisms are not fully identified, we investigated cobalt toxicity in a model human keratinocyte cell line, HaCaT. In this study, we propose a model to determine the in vitro chemical impact on cell viability of a soluble form of cobalt (CoCl{sub 2}) with or without gamma-ray doses to mimic contamination by {sup 60}Co, to elucidate the mechanisms of cobalt intracellular chemical and radiological toxicity. Intracellular cobalt concentration was determined after HaCaT cell contamination and chemical toxicity was evaluated in terms of cellular viability and clonogenic survival. We investigated damage to DNA in HaCaT cells by combined treatment with chemical cobalt and a moderate gamma-ray dose. Additive effects of cobalt and irradiation were demonstrated. The underlying mechanism of cobalt toxicity is not clearly established, but our results seem to indicate that the toxicity of Co(II) and of irradiation arises from production of reactive oxygen species. (authors)

  18. Ligand field effects in the nuclear magnetic shielding of nitrogen-15 and cobalt-59 in bent nitrosyl complexes of cobalt(III)

    International Nuclear Information System (INIS)

    Duffin, P.A.; Larkworthy, L.F.; Mason, J.; Stephens, A.N.; Thompson, R.M.

    1987-01-01

    A range of square-pyramidal complexes of cobalt(III) with a bent apical nitrosyl ligand has been prepared and examined by 15 N and 59 Co NMR spectroscopy, in a study of nephelauxetic and spectrochemical effects at the metal and nitrogen nuclei in the bent Co-NO chromophore. The basal ligands in this comparison include dithiocarbamate, quadridentate Schiff base or porphine, and bis-chelating diamine or oximate, so as to give S 4 , S 2 N 2 , N 4 , OONN, or ONON coordination in the plane and a range of substituents in the chelate and phenylene rings. The shielding of both cobalt and nitrogen tends to decrease with decrease in the M(d) → π*(NO) back-bonding, as indicated by the MN and NO bond distances, the MNO angle and the NO stretching frequency. The shieldings decrease from sulfur to nitrogen to oxygen coligators and also with electron withdrawal by ring substituents (and vice versa), i.e. with decrease in the ligand field splitting and in the nephelauxetism of the coligands. These parallelisms of the cobalt and nitrogen shielding accord with the orbital theory that was developed to explain the bending of the MNO ligand and influences of the metal and coligands. Significant interdependence of spectrochemical and nephelauxetic effects at cobalt and nitrogen arises from the degree of overlap and similarity in energies of the frontier orbitals for the paramagnetic circulation at nitrogen [n(N) → π* (NO)] and at cobalt (d-d). 43 references, 5 figures, 2 tables

  19. Anticancer Gold N-Heterocyclic Carbene Complexes: A Comparative in vitro and ex vivo Study.

    Science.gov (United States)

    Estrada-Ortiz, Natalia; Guarra, Federica; de Graaf, Inge A M; Marchetti, Lorella; de Jager, Marina H; Groothuis, Geny M M; Gabbiani, Chiara; Casini, Angela

    2017-09-07

    A series of organometallic Au I N-heterocyclic carbene (NHC) complexes was synthesized and characterized for anticancer activity in four human cancer cell lines. The compounds' toxicity in healthy tissue was determined using precision-cut kidney slices (PCKS) as a tool to determine the potential selectivity of the gold complexes ex vivo. All evaluated compounds presented cytotoxic activity toward the cancer cells in the nano- or low micromolar range. The mixed Au I NHC complex, (tert-butylethynyl)-1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I), bearing an alkynyl moiety as ancillary ligand, showed high cytotoxicity in cancer cells in vitro, while being barely toxic in healthy rat kidney tissues. The obtained results open new perspectives toward the design of mixed NHC-alkynyl gold complexes for cancer therapy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Zirconia- versus metal-based, implant-supported abutments and crowns

    DEFF Research Database (Denmark)

    Hosseini, Mandana

    , the selection of restoration materials should be based on proper optical characteristics in addition to biocompatibility and sufficient strength of materials. Abutments and crowns based on zirconia are one of the most recent alternatives to metal abutments and metal-ceramic crowns. To date, only few comparative...... and to estimate long-term biomechanical results of zirconia-based versus metal-based restorations. The aim of study I was to analyse the mode of fracture and number of cyclic loadings until veneering fracture of zirconia-based all-ceramic restorations compared to metal-ceramic restorations. The aim of study II...... was to test the reliability and validity of six aesthetic parameters used at the Copenhagen Dental School to assess the aesthetic outcome of implant-supported restorations. The aims of study III and IV were to compare the influence of different abutment and crown materials on biological, biomechanical...