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.

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.

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.

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.

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.

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.)

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.

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.

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.

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

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.

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.

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.

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

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

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)

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.

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...

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°.

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

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

{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.

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.

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

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

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.

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.

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.

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.

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.

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

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.

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.

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.

Alkali-crown ether complexes at metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

2010-07-01

Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

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.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

Science.gov (United States)

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

2017-02-01

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

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

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...

A multi-target caffeine derived rhodium(i) N-heterocyclic carbene complex: evaluation of the mechanism of action.

Science.gov (United States)

Zhang, Jing-Jing; Muenzner, Julienne K; Abu El Maaty, Mohamed A; Karge, Bianka; Schobert, Rainer; Wölfl, Stefan; Ott, Ingo

2016-08-16

A rhodium(i) and a ruthenium(ii) complex with a caffeine derived N-heterocyclic carbene (NHC) ligand were biologically investigated as organometallic conjugates consisting of a metal center and a naturally occurring moiety. While the ruthenium(ii) complex was largely inactive, the rhodium(i) NHC complex displayed selective cytotoxicity and significant anti-metastatic and in vivo anti-vascular activities and acted as both a mammalian and an E. coli thioredoxin reductase inhibitor. In HCT-116 cells it increased the reactive oxygen species level, leading to DNA damage, and it induced cell cycle arrest, decreased the mitochondrial membrane potential, and triggered apoptosis. This rhodium(i) NHC derivative thus represents a multi-target compound with promising anti-cancer potential.

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

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.

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.

Crystal structures of dioxonium hexafluorotantalate and dioxonium hexafluoroniobate complexes with tetrabenzo-30-crown-10

Energy Technology Data Exchange (ETDEWEB)

Furmanova, N. G., E-mail: furm@ns.crys.ras.ru; Rabadanov, M. Kh.; Chernaya, T. S. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Fonari, M. S., E-mail: fonari.xray@phys.asm.md; Simonov, Yu. A. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Ganin, E. V., E-mail: edganin@yahoo.com [Ministry of Education and Science and National Academy of Sciences of Ukraine, Odessa State Environmental University (Ukraine); Gelmboldt, V. O., E-mail: eksvar@ukr.net [Ministry of Education and Science and National Academy of Sciences of Ukraine, Physicochemical Institute for Human and Environmental Protection (Ukraine); Grigorash, R. Ya.; Kotlyar, S. A.; Kamalov, G. L., E-mail: kamalov@ukr.net.ua [National Academy of Sciences of Ukraine, Bogatsky Physicochemical Institute (Ukraine)

2008-03-15

Two isostructural complexes of dioxonium [H{sub 5}O{sub 2}]{sup +} with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 {center_dot} H{sub 5}O{sub 2})][TaF{sub 6}] (I) and [(tetrabenzo-30-crown-10 {center_dot} H{sub 5}O{sub 2})][NbF{sub 6}] (II) are studied using X-ray diffraction. The complexes crystallize in the monoclinic crystal system (space group C2/c, Z = 4). The unit cell parameters of these compounds are as follows: a = 15.6583(12) Angstrom-Sign , b = 15.2259(13) Angstrom-Sign , c = 16.4473(13) Angstrom-Sign , and {beta} = 99.398(6) Degree-Sign for complex I and a = 15.7117(12) Angstrom-Sign , b = 15.2785(15) Angstrom-Sign , c = 16.5247(15) Angstrom-Sign , and {beta} = 99.398(7) Degree-Sign for complex II. These complexes belong to the ionic type. The dioxonium cation [H{sub 5}O{sub 2}]{sup +} in the form of the two-unit cluster [H{sub 3}O {center_dot} H{sub 2}O]{sup +} is stabilized by the strong hydrogen bond OH Midline-Horizontal-Ellipsis O [O Midline-Horizontal-Ellipsis O, 2.353(4) Angstrom-Sign ] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O Midline-Horizontal-Ellipsis O(crown). The crown ether adopts an unusual two-level (pocket-like) conformation, which provides a complete encapsulation of the oxonium associate. The interaction of the cationic complex with the anion in the crystal occurs through contacts of the C-H Midline-Horizontal-Ellipsis F type.

18-Crown-6-polyether complexing with iodine

International Nuclear Information System (INIS)

Borovikov, Yu.Ya.

1988-01-01

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

18-Crown-6-polyether complexing with iodine

Energy Technology Data Exchange (ETDEWEB)

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

1988-01-01

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

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...

Carbynes and carbenes in coordination chemistry: A new class of pentaammine and tetraammine complexes of osmium(II)

Energy Technology Data Exchange (ETDEWEB)

Hodges, L.M.; Sabat, M.; Harman, W.D. (Univ. of Virginia, Charlottesville (United States))

1993-02-17

Since their discovery by Fischer and co-workers in 1973, the study of transition-metal carbyne complexes and their role in alkyne metathesis has rapidly developed into a mature field. Although carbyne complexes are known for a diverse set of early- and mid-transition metals, the vast majority of these complexes contain carbon or phosphine [pi]-acids, or bulky alkoxide ligands, which limit the coordination number. We wish to report the first example of a carbyne species, as well as several heteroatom-carbene derivatives, in which the metal fragment, Os[sup II](NH[sub 3])[sub 5], provides a classical octahedral coordination environment. The carbyne [Os(NH[sub 3])[sub 5]([equivalent to]CPh)](OTf)[sub 3] (2) is synthesized in two steps from Os(NH[sub 3])[sub 5](OTf)[sub 3] and benzaledhyde dimethyl acetal.

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

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.

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,

Hydrogen bonding assemblies in host guest complexes with 18-crown-6

Science.gov (United States)

Fonari, M. S.; Simonov, Yu. A.; Kravtsov, V. Ch.; Lipkowski, J.; Ganin, E. V.; Yavolovskii, A. A.

2003-02-01

Recent X-ray crystal structural data for two novel 1:2 host-guest complexes of 18-crown-6 with neutral organic molecules, thiaamide hydrazide of 2-aminobenzoic acid and thiaamide hydrazide of 4-amino-1,2,5-thiadiazole-3-carbonic acid are reported. The supramolecular structures of these two and five relative complexes are discussed from the point of view of participation of donor groups in coordination with the crown ether, and donor and acceptor groups in the self-assembly of the guest molecules. Guest molecules have incorporated amine and hydrazine moieties as proton donors and carbonyl oxygen and sulfur (in thiadiazole and in thiaamine moieties) as proton acceptors. The guest-guest interactions appeared to be crucial in the final architecture.

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.

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

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.

Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

Science.gov (United States)

Ison, Elon A.; Ison, Ana

2012-01-01

A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

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

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.

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

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.

Biological Screening of Newly Synthesized BIAN N-Heterocyclic Gold Carbene Complexes in Zebrafish Embryos

Science.gov (United States)

Farooq, Muhammad; Abu Taha, Nael; Butorac, Rachel R.; Evans, Daniel Anthony; Elzatahry, Ahmed A.; Elsayed, Elsayed Ahmed; Wadaan, Mohammad A. M.; Al-Deyab, Salem S.; Cowley, Alan H.

2015-01-01

N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10–12 h. One hundred percent mortality was observed at concentrations ≥50 µM. At sub-lethal concentrations (10–30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%–40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules. PMID:26501273

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.

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

NARCIS (Netherlands)

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

1987-01-01

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

Kinetically inert lanthanide complexes as reporter groups for binding of potassium by 18-crown-6

DEFF Research Database (Denmark)

Junker, Anne Kathrine Ravnsborg; Tropiano, Manuel; Faulkner, Stephen

2016-01-01

in a copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) “click” reaction with azide-functionalized crown ethers. The resulting complexes were investigated using NMR and optical methods. Titrations with potassium chloride in methanol observing the sensititzed europium- and terbium-centered emissions were......-centered emission to report on the binding of potassium in an 18-crown-6 binding pocket. The responsive systems were made by linking a crown ether to a kinetically inert lanthanide binding pocket using a molecular building block approach. Specifically, an alkyne-appended Ln.DO3A was used as a building block...... used to investigate the response of the systems. The molecular reporters based on aliphatic crown ethers were found to have strongly inhibited binding of potassium, while the benzo-18-crown-6 derived systems had essentially the same association constants as the native crown ethers. The shape...

Rhenium(5) and molybdenum(5) complexes with 4',4(5)-divaleryldibenzo-18-crown-6

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.; Tashmukhamedova, A.K.; Basitova, S.M.

1993-01-01

Methods for synthesizing oxohalide complexes of rhenium and molybdenum with +5 oxidation degree with 4',4 (5) -divaleryldibenzo-18-crown-6 were developed. Content and composition of prepared compounds were investigated by the methods of element analysis, crystal optics, conductometry, IR spectroscopy in the near and far regions, thermogravimetry. Oxidation degree of the complex-forming metal was determined. It was established that composition of the compounds coressponded to the general formula MOLX · H 2 O, where M - Re, Mo; L -4',4 (5) -divaleryldibenzo-18-crown-6; X -Cl - , Br -

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.

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

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

A chemical-biological evaluation of rhodium(I) N-heterocyclic carbene complexes as prospective anticancer drugs.

Science.gov (United States)

Oehninger, Luciano; Küster, Laura Nadine; Schmidt, Claudia; Muñoz-Castro, Alvaro; Prokop, Aram; Ott, Ingo

2013-12-23

Rhodium(I) complexes bearing N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of these organometallics. A series of Rh(I)-NHC derivatives with 1,5-cyclooctadiene and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with moderate inhibitory activity of thioredoxin reductase (TrxR) and efficient binding to biomolecules (DNA, albumin). Biodistribution studies showed that the presence of albumin lowered the cellular uptake and confirmed the transport of rhodium into the nuclei. Changes in the mitochondrial membrane potential (MMP) were observed as well as DNA fragmentation in wild-type and daunorubicin- or vincristine-resistant Nalm-6 leukemia cells. Overall, these studies indicated that Rh(I)-NHC fragments could be used as partial structures of new antitumor agents, in particular in those drugs designed to address resistant malignant tissues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

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

International Nuclear Information System (INIS)

Rounaghi, G.; Popov, A.I.

1986-01-01

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

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.

Synthesis, photo-, and electrochemistry of ruthenium bis(bipyridine) complexes comprising a N-heterocyclic carbene ligand.

Science.gov (United States)

Leigh, Vivienne; Ghattas, Wadih; Lalrempuia, Ralte; Müller-Bunz, Helge; Pryce, Mary T; Albrecht, Martin

2013-05-06

Analogues of [Ru(bpy)3](2+) were prepared in which one pyridine ligand site is substituted by a N-heterocyclic carbene (NHC) ligand, that is, either by an imidazolylidene with a variable wingtip group R (R = Me, 3a; R = Et, 3b; R = iPr, 3c), or by a benzimidazolylidene (Me wingtip group, 3d), or by a 1,2,3-triazolylidene (Me wingtip group, 3e). All complexes were characterized spectroscopically, photophysically, and electrochemically. An increase of the size of the wingtip groups from Me to Et or iPr groups distorts the octahedral geometry (NMR spectroscopy) and curtails the reversibility of the ruthenium oxidation. NHC ligands with methyl wingtip groups display reversible ruthenium oxidation at a potential that reflects the donor properties of the NHC ligand (triazolylidene > imidazolylidene > benzimidazolylidene). The most attractive properties were measured for the triazolylidene ruthenium complex 3e, featuring the smallest gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the series (2.41 eV), a slightly red-shifted absorption profile, and reasonable excited-state lifetime (188 ns) when compared to [Ru(bpy)3](2+). These features demonstrate the potential utility of triazolylidene ruthenium complexes as photosensitizers for solar energy conversion.

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

KAUST Repository

Gó mez-Herrera, Alberto; Nahra, Fady; Brill, Marcel; Nolan, Steven P.; Cazin, Catherine S. J.

2016-01-01

The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

KAUST Repository

Gómez-Herrera, Alberto

2016-08-22

The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

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

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.

Features of E-Z-photoisomerization reversible reaction of 4-styrylpyridine crown-containing complexes with different cations

International Nuclear Information System (INIS)

Fedorov, Yu.V.; Shepel', N.Eh.; Chernikova, E.Yu.; Fedorova, O.A.; Gulakova, E.N.; Avakyan, V.G.; Jonushauskas, G.

2008-01-01

E-Z-Photoisomerization reversible reaction of crown-containing 4-styrylpyridine in the presence of alkali metal perchlorates (Ca 2+ , Mg 2+ , Ba 2+ ) gifted in the formation of complexes with crown-ether fragments, as well as heavy metal perchlorates (Hg 2+ , Cd 2+ ) gifted in the coordination with nitrogen atom of heterocyclic residuum has been studied. Effect of complexing on the photoisomerization is determined by electron spectroscopy and NMR 1 H, structures of the formed Z-isomers are established. The possibility of the E-Z-isomerization control with the use of supramolecular complexing is confirmed by the investigations [ru

On the mechanism of imine elimination from Fischer tungsten carbene complexes

Directory of Open Access Journals (Sweden)

Philipp Veit

2016-06-01

Full Text Available (Aminoferrocenyl(ferrocenylcarbene(pentacarbonyltungsten(0 (CO5W=C(NHFcFc (W(CO5(E-2 is synthesized by nucleophilic substitution of the ethoxy group of (CO5W=C(OEtFc (M(CO5(1Et by ferrocenyl amide Fc-NH– (Fc = ferrocenyl. W(CO5(E-2 thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3 via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO5(E-2 decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG‡298K = 112 kJ mol−1. Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent densitiy functional theory [(TD-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II intermediates cis(N,H-W(CO4(H(Z-15 and cis(C,H-W(CO4(H(Z-15.

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

Energy Technology Data Exchange (ETDEWEB)

Rounaghi, G.; Popov, A.I.

1986-01-01

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

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,

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.

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.

Human colon cancer targeted pro-apoptotic, anti-metastatic and cytostatic effects of binuclear Silver(I)-N-Heterocyclic carbene (NHC) complexes.

Science.gov (United States)

Asif, Muhammad; Iqbal, Muhammad Adnan; Hussein, Mouayed A; Oon, Chern Ein; Haque, Rosenani A; Khadeer Ahamed, Mohamed B; Abdul Majid, Aman Shah; Abdul Majid, Amin Malik Shah

2016-01-27

The current mechanistic study was conducted to explore the effects of increased lipophilicity of binuclear silver(I)-NHC complexes on cytotoxicity. Two new silver(I)-N-Heterocyclic Carbene (NHC) complexes (3 and 4), having lypophilic terminal alkyl chains (Octyl and Decyl), were derived from meta-xylyl linked bis-benzimidazolium salts (1 and 2). Each of the synthesized compounds was characterized by microanalysis and spectroscopic techniques. The complexes were tested for their cytotoxicity against a panel of human cancer c as well normal cell lines using MTT assay. Based on MTT assay results, complex 4 was found to be selectively toxic towards human colorectal carcinoma cell line (HCT 116). Complex 4 was further studied in detail to explore the mechanism of cell death and findings of the study revealed that complex 4 has promising pro-apoptotic and anti-metastatic activities against HCT 116 cells. Furthermore, it showed pronounced cytostatic effects in HCT 116 multicellular spheroid model. Hence, binuclear silver(I)-NHC complexes with longer terminal aliphatic chains have worth to be further studied against human colon cancer for the purpose of drug development. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Mass spectra of alkaline earth salts with a FAB source. Complexation with crown ethers

International Nuclear Information System (INIS)

Ulrich, J.

1987-01-01

With a liquid desorption FAB source it is possible to obtain alkaline earth metal ions complexed by a crown ether. Conditions for formation of these complexes ions are examined for selection of the complexing agent in function of cation size. Behaviour of alkaline and alkaline earth compounds are compared allowing the differentiation of ion extraction phenomena by liquid desorption ion source and solvent extraction [fr

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.

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.

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

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.

STRUCTURE AND THERMAL STABILITY OF THE BENZO-15-CROWN-5 WITH LANTHANUM (III BROMIDE COMPLEX

Directory of Open Access Journals (Sweden)

Muhammad Idiris Saleh

2010-06-01

Full Text Available The reaction of benzo-15-crown-5 (C14H20O5 ligand with La(NO33.7H2O in the presence of HBr has resulted in the production of an exotic sandwich complex, [LaC28H36Br4O10][3Br]. The crystal system is triclinic with space group P1, a = 12.5834(14 Å, b = 13.5816(16 Å, c = 13.8403(16 Å, a = 70.751(2°, b = 66.773(2° and g = 67.631(2°. The cation comprises of the lanthanum atom coordinated to two crowns via three oxygen atoms from each crown in a η3-sandwich fashion. The two phenyl groups of the crown are brominated. The La-OLigand bond lengths are between 2.857(7 and 2.949(7 Å. The trianion [3Br]3- is linear with Br-Br bond lengths of 2.518(2 and 2.560(2 Å respectively. The molecule is stabilized by intermolecular interactions of the type C-H...Br to form dimers and are arranged parallel to bc face.  Keywords: lanthanum, benzo-15-crown-5, hydrogen bonding, bromination, x-ray structure

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....

(VI) ML6 Complexes

African Journals Online (AJOL)

A geometric analysis revealed that beta-(C-H) and alpha-(C-C) can occupy the seventh and eighth coordination sites in the title Fischer carbene complexes as agostic interactions, which allows classifying the carbene as a η3 ligand in these cases. This theory was supported by the relative energies of the conformers and an ...

The antimicrobial efficacy of sustained release silver–carbene complex-loaded l-tyrosine polyphosphate nanoparticles: Characterization, in vitro and in vivo studies

Science.gov (United States)

Hindi, Khadijah M.; Ditto, Andrew J.; Panzner, Matthew J.; Medvetz, Douglas A.; Han, Daniel S.; Hovis, Christine E.; Hilliard, Julia K.; Taylor, Jane B.; Yun, Yang H.; Cannon, Carolyn L.; Youngs, Wiley J.

2009-01-01

The pressing need to treat multi-drug resistant bacteria in the chronically infected lungs of cystic fibrosis (CF) patients has given rise to novel nebulized antimicrobials. We have synthesized a silver–carbene complex (SCC10) active against a variety of bacterial strains associated with CF and chronic lung infections. Our studies have demonstrated that SCC10-loaded into l-tyrosine polyphosphate nanoparticles (LTP NPs) exhibits excellent antimicrobial activity in vitro and in vivo against the CF relevant bacteria Pseudomonas aeruginosa. Encapsulation of SCC10 in LTP NPs provides sustained release of the antimicrobial over the course of several days translating into efficacious results in vivo with only two administered doses over a 72 h period. PMID:19395021

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

Rhenium (5) and molybdenum (5) complexes with 4',4''(5'')-ditretbutyldibenzo-24-crown-8

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.; Basitova, S.M.; Tashmukhamedova, A.K.; Sajfullina, N.Zh.

1989-01-01

Rhenium and molybdenum complexes in +5 oxidation degree with 4',4''(5'')-ditretbutyldibenzo-24-crown-8 (L) are synthesized with 75-95 % yield. Composition and structure of compounds produced are investigated using element analysis, conductometry, IR spectroscopy, thermogravimetry methods. Oxidation degree of complexer metal is determined. It is ascertained that the compound composition corresponds to the MOLX 3 formula, where M-Re, Mo; X-Cl - , Br -

ESR investigation of alkali metal complexes of galvinoxyl-labeled benzo-15-crown-5 in frozen solution

International Nuclear Information System (INIS)

Mukai, Kazuo; Iida, Nobuhito; Ishizu, Kazuhiko

1982-01-01

A stable galvinoxyl derivative (1) of benzo-15-crown-5 was prepared and the complex formation between the spin labeled crown ether 1 and the alkali metal and ammonium salts was studied by the ESR technique. Existence of the (2:1) complex of 1 with potassium, rubidium, and ammonium salts was confirmed by the observation of the triplet ESR spectra in ethanol rigid matrix at 77K. Essentially the same g- and D-tensor values are observed for all the (2:1) complexes, indicating similar conformation of the ligand mole cule 1. The zero-field splitting parameters (D and E) are calculated on the basis of the spin distribution of 1 and the assumed molecular structures for the (2:1) complex. By comparing the observed D and E parameters with the calculated ones, the structure of the (2:1) complex in ethanol rigid matrix is discussed. On the other hand, the sodium complexes of 1 show a slightly asymmetric single line, suggesting the (1:1) complex formation btween 1 and the sodium salts. No anions (SCN - , Br - , and I - ) have any appreciable effect on the ESR spectra of both the (2:1) and (1:1) complexes. (author)

Stability of the barium–benzo-15-crown-5 complex in nitrobenzene saturated with water

Directory of Open Access Journals (Sweden)

E. MAKRLÍK

2006-11-01

Full Text Available From extraction experiments and g-activity measurements, the exchange extraction constant corresponding to the equilibrium Ba2+(aq + SrL22+(nb D BaL22+(nb + Sr2+(aq occurring in the two-phase water–nitrobenzene system (L =benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase was evaluated as log Kex (Ba2+, SrL22+ = 0.3 ± 0.1. Furthermore, the stability constant of the benzo-15-crown-5–barium complex in nitrobenzene saturated with water was calculated for the temperature of 25 °C: log bnb (BaL22+=13.3±0.1.

Investigation of iron(III) complex with crown-porphyrin

Energy Technology Data Exchange (ETDEWEB)

Pankratov, Denis A., E-mail: pankratov@radio.chem.msu.ru; Dolzhenko, Vladimir D. [Lomonosov Moscow State University (Russian Federation); Stukan, Reonald A. [Semenov Institute of Chemical Physics, Russian Academy of Sciences (Russian Federation); Al Ansari, Yana F.; Savinkina, Elena V. [Lomonosov Moscow State Academy of Fine Chemical Technology (Russian Federation); Kiselev, Yury M. [Lomonosov Moscow State University (Russian Federation)

2013-08-15

Iron complex of 5-(4-(((4 Prime -hydroxy-benzo-15-crown-5)-5 Prime -yl)diazo)phenyl)-10,15, 20-triphenylporphyrin was investigated by {sup 57}Fe Moessbauer spectroscopy and EPR. Two Fe sites were identified; they give two differing signals, doublet and wide absorption in a large velocity interval. EPR spectra of solutions of the complex in chloroform at room temperature also show two signals with g = 2.064, A{sub Fe} = 0.032 cm{sup - 1}; g = 2.015, A{sub Fe} = 0.0034 cm{sup - 1}. The doublet asymmetry is studied vs. temperature and normal angle to the sample plane and gamma-beam. The isomer shift {delta} in the doublet varies from 0.25 to 0.41 mm/s in the 360-5 K temperature range, whereas quadruple splitting value is constant, {Delta} {approx} 0.65 mm/s. The relax absorption may be described as a wide singlet ({delta} = 0.30- 0.44 mm/s and {Gamma} = 2.83-3.38 mm/s); its relative area strongly depends on temperature. According to {delta}, both signals are assigned to Fe(III)

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.

Synthesis and characterization of nitrile functionalized silver(I)-N-heterocyclic carbene complexes: DNA binding, cleavage studies, antibacterial properties and mosquitocidal activity against the dengue vector, Aedes albopictus.

Science.gov (United States)

Asekunowo, Patrick O; Haque, Rosenani A; Razali, Mohd R; Avicor, Silas W; Wajidi, Mustafa F F

2018-04-25

A series of four benzimidazolium based nitrile-functionalized mononuclear-Ag(I)-N-heterocyclic carbene and binuclear-Ag(I)-N-heterocyclic carbene (Ag(I)-NHC) hexafluorophosphate complexes (5b-8b) were synthesized by reacting the corresponding hexafluorophosphate salts (1b-4b) with Ag 2 O in acetonitrile, respectively. These compounds were characterized by 1 H NMR, 13 C NMR, IR, UV-visible spectroscopic techniques, elemental analyses and molar conductivity. Additionally, 8b was structurally characterized by single crystal X-ray diffraction technique. Preliminary in vitro antibacterial evaluation was conducted for all the compounds against two standard bacteria; gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacterial strains. Most of the Ag(I)-NHC complexes (5b-8b) showed moderate to good antibacterial activity with MIC values in the range of 12.5-100 μg/mL. Especially, compound 8b exhibited promising anti-Staphylococcus aureus activity with a low MIC value (12.5 μg/mL). However, all the hexafluorophosphate salts (1b-4b) were inactive against the bacteria strains. The preliminary interactive investigation revealed that the most active compound, 8b, could effectively intercalate into DNA to form 8b-DNA complex which shows a better binding ability for DNA (K b  = 3.627 × 10 6 ) than the complexes 5b-7b (2.177 × 10 6 , 8.672 × 10 5 and 6.665 × 10 5 , respectively). Nuclease activity of the complexes on plasmid DNA and Aedes albopictus genomic DNA was time-dependent, although minimal. The complexes were larvicidal to the mosquito, with 5b, 6b and 8b being highly active. Developmental progression from the larval to the adult stage was affected by the complexes, progressively being toxic to the insect's development with increasing concentration. These indicate the potential use of these complexes as control agents against bacteria and the dengue mosquito Ae. albopictus. Copyright © 2018 Elsevier Masson SAS. All

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.

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.

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

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.

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

Structural investigation of 18-crown-6 complexes of Tri organotin carboxylate by 1H, 13C, 19F and 119Sn nuclear magnetic resonance spectroscopy

International Nuclear Information System (INIS)

Foladi, S.; Yousefi, M.; Mohammadpour Ammini, M. M.

2002-01-01

Single crystal structure determination of several 18-crown 6 complexes of orga nation derivatives reveals formation of aqua complex through hydrogen bonding to 18-crown-6, which is an important feature in their structure. In the majority of those studies, mono- and dichloro organotin have been used for complexation of them with crown ethers. In the present work, several 18-crown 6 complexes of tri organotin acetate[(C 6 H 5 ) 3 SnOCOCX 3 ] 2 , 18 C6 ], X=F, Cl, and H, have been prepared. The Lewis acidity of tin moiety in tri organotin carboxylate have been tailored by replacing hydrogen atoms of acetate group with chlorine and fluorine and influence of them in the formation of aqua complex with 18 C6 have been studied by infrared. 1 H, 13 C, 19 F and 119 Sn nuclear magnetic resonance spectroscopes. The effects of coordinating and non-coordinating solvent in status of structure in solution have been explored

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.

Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes.

Science.gov (United States)

Ornelas-Megiatto, Cátia; Shah, Parth N; Wich, Peter R; Cohen, Jessica L; Tagaev, Jasur A; Smolen, Justin A; Wright, Brian D; Panzner, Matthew J; Youngs, Wiley J; Fréchet, Jean M J; Cannon, Carolyn L

2012-11-05

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH(2)Cl(2) (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery.

Synthesis, characterization and properties of novel amide derivatives based open-chain crown ether and their Tb (III) complexes

International Nuclear Information System (INIS)

Liu, Yanhong; He, Wei; Yang, Zehui; Chen, Yanwen; Wang, Xinwei; Guo, Dongcai

2015-01-01

Six amide-based open-chain crown ether and their solid complexes with terbium nitrates were synthesized. The target complexes were characterized by elemental analysis, mass spectra, EDTA titrimetric analysis, thermal analysis, molar conductivity, infrared spectra and UV–vis spectra. Luminescence properties of the ligands and the corresponding complexes in solid were studied. The results showed that the introduction of electron-donating group to the ligand enhanced the luminescence intensity of the corresponding complex, but electron-withdrawing group conversely. Meanwhile, among all complexes, the luminescence quantum yield of the complex Tb(NO 3 ) 3 Y 1 was highest up to 0.76. Electrochemical properties were also investigated, and the results showed that the introduction of electron-donating group to the ligand enhanced the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO) energy level, but electron-withdrawing group conversely. And these target complexes may possibly be useful for studying in organic light-emitting devices field. - Highlights: • Novel amide derivatives based open-chain crown ether and their Tb (III) complexes were prepared and characterized. • The target complexes presented high thermodynamic stability. • Influence of the substituent on luminescence intensity and electrochemical property were discussed

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

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…

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.

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.

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.

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.

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.

Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes

KAUST Repository

Ornelas-Megiatto, Cá tia; Shah, Parth N.; Wich, Peter R.; Cohen, Jessica L.; Tagaev, Jasur A.; Smolen, Justin A.; Wright, Brian D.; Panzner, Matthew J.; Youngs, Wiley J.; Frechet, Jean; Cannon, Carolyn L.

2012-01-01

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH2Cl2 (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery. © 2012 American Chemical Society.

Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes

KAUST Repository

Ornelas-Megiatto, Cátia

2012-11-05

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH2Cl2 (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery. © 2012 American Chemical Society.

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)

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

Science.gov (United States)

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

2013-11-01

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

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)

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.

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.

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.

Modeling a calixarene-crown-6 and its alkali complexes by means of a hybrid quantum mechanical/molecular mechanical method

International Nuclear Information System (INIS)

Lamare, V.; Golebiowski, J.; Ruiz-Lopez, M.F.; Martins-Costa, M.; Millot, C.

2000-01-01

Calixarene-crown-6s in 1,3-alternate conformation are compounds currently investigated for their ability to selectively extract traces of cesium from acidic or strong salinity aqueous solutions. Studies based on molecular modeling were undertaken on these systems to understand their behavior regarding cesium and other alkali cations, in particular sodium. In this work, a recently developed molecular modeling approach was used to investigate calixarene BC6 and its alkali complexes. The whole calixarene ligand is treated by the semiempirical AM1 quantum method (QM) whereas the cation and solvent are treated by a conventional force field (MM). The total energy of the system is the sum of the QM and MM sub-system contributions plus the QM/MM interaction energy. The latter includes the electrostatic interaction between QM charges (nuclei + electrons) and MM sites, and the non-electrostatic QM/MM van der Weals term, usually expressed by a Lennard-Jones potential. In the QM/MM method, van der Waals interactions between the QM and MM sub-systems are described by empirical Lennard-Jones parameters which must be adapted to the hybrid potential considered. Parameters on oxygen atoms were optimized. For the cations, two sets of Parameters were tested: Aqvist empirical parameters, derived to represent cation/water interactions in classical dynamics (set 2), and a new set of parameters which we calculated from dispersion coefficients available in the literature (set 1). The latter gave better results for the interactions with the crown. In the sodium complex, the cation interacts with only four oxygen atoms of the crown, whereas in the complex with cesium, the interaction involves six oxygen atoms. Distortion of the BC6 is therefore less with sodium and favors the corresponding complex by 4 kcal/mol. The cation/BC6 van der Waals energy is very weak for the two complexes. Hence the interaction between the cation and BC6 is primarily electrostatic. The BC6 polarization energy due

Selenophene transition metal complexes

Energy Technology Data Exchange (ETDEWEB)

White, Carter James [Iowa State Univ., Ames, IA (United States)

1994-07-27

This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η⁵- and the η¹(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The ⁷⁷Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η¹(S)-bound thiophenes, η¹(S)-benzothiophene and η¹(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η¹(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh₃)Re(2-benzothioenylcarbene)]O₃SCF₃ was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η¹(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

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.

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.

Carbene complexes of zirconium. Synthesis, structure, and reactivity with carbon monoxide to affort coordinated ketene

International Nuclear Information System (INIS)

Barger, P.T.; Santarsiero, B.D.; Armantrout, J.; Bercaw, J.E.

1984-01-01

Treatment of Cp 2 Zr(L)(CO) (Cp = C 5 H 5 ; L = PMe 3 , CO) with Cp* 2 ZrH 2 (Cp* = C 5 Me 5 ) affords zirconium oxycarbene complexes, Cp 2 (L)Zr double bond CHO single bond Zr(X)Cp* 2 (L = PMe 3 , X = H, I; L = CO, X = H), that represent some of the first examples of group 4 metal-to-carbon multiple bonding. The first X-ray diffraction structure determination of a zirconium carbene complex, that of Cp(PMe 3 )Zr double bond CHO single bond Zr(H)Cp* 2 .C 6 H 6 , is reported (C2/c, a = 27.318 (4) A, b = 19.895 (3) A, c = 19.932 (5) A β = 132.188 (10) 0 , Z = 8) and shows a very short Zr-C bond length of 2.117 (7) A. Treatment of Cp 2 (CO)Zr double bond CHO single bond Zr(H)Cp* 2 with CH 3 I or Cp 2 (PMe 3 )Zr double bond CHO single bond Zr(I)Cp* 2 with CO affords the zirconium substituted enediolate zirconacycle, Cp* 2 ZrOCH double bond C(Zr(I)Cp 2 )O, which has been characterized by an X-ray diffraction study (P2 1 /c, a = 15.866 (4) A, b = 10.673 (3) A, c = 20.561 (4) A, β = 105.5 (2) 0 , Z = 4). This complex most likely forms by coupling of the zirconoxycarbene and a carbonyl to give a metal-coordinated ketene intermediate that subsequently rearranges to the isolated product. An isotopic crossover experiment has demonstrated that the new carbon-carbon bond is formed in an intramolecular coupling step. The ketene intermediate can be trapped by dissolving Cp 2 (CO)Zr double bond CHO single bond Zr(H)Cp* 2 in pyridine, giving Cp 2 (py)Zr(O double bond C double bond CHOZr(I)Cp* 2 ). Treatment of the isolated ketene complex with CH 3 I in benzene gives the enediolate zirconocycle; in pyridine Cp 2 (py)Zr(O double bond C double bond CHOZr(I)Cp* 2 ) can be observed spectroscopically. 38 references, 4 figures, 5 tables

Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

KAUST Repository

Jothibasu, Ramasamy

2010-09-13

Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

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.

Design, synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes. The effect of crown ether hydrophilic substituents.

Science.gov (United States)

Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin

2009-01-05

Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10

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.

Experimental and theoretical study on the complexation of the thallium cation with dibenzo-18-crown-6

Czech Academy of Sciences Publication Activity Database

Makrlík, E.; Toman, Petr; Vaňura, P.

2012-01-01

Roč. 59, č. 1 (2012), s. 199-202 ISSN 1318-0207 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505 Keywords : thallium cation * dibenzo-18-crown-6 * complexation, Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.135, year: 2012 http://acta.chem-soc.si/59/59-1-199.pdf

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.

Coprecipitation of 137Cs and 85Sr microquantities with complex compound [M(18-crown-6)]BPH4 (M=Na+, Cs+) from neutral and alkaline solutions

International Nuclear Information System (INIS)

Konovalova, N.A.; Rumer, I.A.; Kulyukhin, S.A.

2009-01-01

The paper reports the possibility of joint separation of 137 Cs and 85 Sr from neutral and alkaline aqueous solutions by their coprecipitation with the solid phase of complex compounds [M(18-crown-6)]BPh 4 (M=Na + , Cs + ), as well as to study the coprecipitation of 137 Cs and 85 Sr with the solid phase CsBPh 4 . It is found that complex compounds [M(18-crown-6)]BPh 4 (M=Na + , Cs + ) increased the degree of 85 Sr separation from solutions virtually two- to threefold vs. CsBPh 4 . Chloride and nitrate were found to have hardly any impact on the coprecipitation of 137 Cs and 85 Sr with [M(18-crown-6)]BPh 4 (M = Na + , Cs + ). (orig.)

H-D exchange in metal carbene complexes: Structure of cluster (μ-H)(μ-OCD3)Os3(CO)9{:C(CD3)NC2H8O}

Science.gov (United States)

Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia

2015-10-01

X-ray and spectroscopic data for the new complex (μ-H)(μ-OCH3)Os3(CO)9{:C(CD3)NC2H8O} (2) obtained in the reaction of the (μ-H)(μ-Cl)Os3(CO)9{:C(CH3)NC2H8O} (1) with NaOCD3 in CD3OD solution are reported. It is shown that cluster 1 has the property of CH-acidity inherent of Fisher type carbenes. This had demonstrated using hydrogen deuterium exchange reaction in the presence of a strong base. Bridging chlorine to metoxide ligand substitution takes place during the reaction. The molecular structure of 2 is compared with known analogues.

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.

Unsaturated carbone and allenylidene ruthenium complexes from alkynes

International Nuclear Information System (INIS)

Bozek, Yu.L.; Diznev, P.A.

1995-01-01

The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

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...

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.

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

Complexation between Methyl Viologen (Paraquat) Bis(Hexafluorophosphate) and Dibenzo[24]Crown-8 Revisited

DEFF Research Database (Denmark)

Gasa, Travis B.; Spruell, Jason M.; Dichtel, William R.

2009-01-01

Paraquat bis(hexafluorophosphate) undergoes stepwise dissociation in acetone. All three species - the neutral molecule, and the mono- and dications - are represented significantly under the experimental conditions typically used in host-guest binding studies. Paraquat forms at least four host...... toward dibenzo[24]crown-8. Thus, the relative abundance of neutral, singly, and doubly charged pseudorotaxanes is identical to the relative abundance of neutral, singly, and doubly charged paraquat unbound with respect to the crown ether in acetone. In the specific case of paraquat/dibenzo[24]crown-8...

Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

Science.gov (United States)

Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

2016-10-06

The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H 2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h -1 and a TON of 449 000 for H 2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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.

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.

Electron pairing analysis of the Fischer-type chromium-carbene complexes (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH )

Energy Technology Data Exchange (ETDEWEB)

Poater, Jordi; Cases, Montserrat; Fradera, Xavier; Duran, Miquel; Sola, Miquel

2003-10-15

The electron-pair density distributions of a series of 25 Fischer carbene complexes of the type (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH) are analyzed using the Atoms in Molecules theory. Localization and delocalization indices are used to characterize the electron pairing taking place in the Cr=C---X moiety in these complexes. Electron delocalization between the Cr and C atoms and between the C atom and the X group are related to the {pi}-donor strength of the X group and the degree of back-donation between the chromium pentacarbonyl and the carbene fragments. The results obtained with the Atoms in Molecules theory complement those obtained in a previous study by means of energy and charge decomposition analyses. Electron delocalization between the Cr atom and the X group is consistent with the hypothesis of a weak 3-center 4-electron bonding interaction in the Cr=C-X group of atoms. Except for X=H, {delta}(Cr,X) increases with the decrease of the {pi}-donor character of the X group.

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.

Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C-60 to Afford Efficient Photodriven Charge Separation

DEFF Research Database (Denmark)

Supur, M.; Kawashima, Y.; Larsen, K. R.

2014-01-01

) obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6-311G(d,p) level, the orbital interactions between the crown ether moieties and the p surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation...

Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

Energy Technology Data Exchange (ETDEWEB)

Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.

2008-01-30

The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

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

International Nuclear Information System (INIS)

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

1984-01-01

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

Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

International Nuclear Information System (INIS)

Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

1992-01-01

To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

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).

Dansyl - Substituted Aza Crown Ethers: Complexation with Alkali, Alkaline Earth Metal Ions and Ammonium

Science.gov (United States)

Deiab, Shihab; Archibong, Edikan; Tasheva, Donka; Mochona, Bereket; Gangapuram, Madhavi; Redda, Kinfe

2011-01-01

The present study investigates the binding properties of four dansyl substituted aza-crown ethers with alkali, alkaline earth metal ions and ammonium. The influence of the solvent polarity and protonation on the photophysical properties of the compounds was studied by UV/Vis and fluorescence methods. The host species caused only slight changes on the absorption spectra of the ligands. The fluorescence changes were more pronounced and concentration dependent thus allowing to calculate the binding constants of the process. The most stable complex under our working conditions was the one between Ba2+ and DNS18C6. PMID:21738561

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

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

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.

Synthesis, structure and DFT conformation analysis of CpNiX(NHC) and NiX2(NHC)2 (X = SPh or Br) complexes

Science.gov (United States)

Malan, Frederick P.; Singleton, Eric; van Rooyen, Petrus H.; Conradie, Jeanet; Landman, Marilé

2017-11-01

The synthesis, density functional theory (DFT) conformational study and structure analysis of novel two-legged piano stool Ni N-heterocyclic carbene (NHC) complexes and square planar Ni bis-N-heterocyclic carbene complexes, all containing either bromido- or thiophenolato ligands, are described. [CpNi(SPh)(NHC)] complexes were obtained from the neutral 18-electron [CpNiBr(NHC)] complexes by substitution of a bromido ligand with SPh, using NEt3 as a base to abstract the proton of HSPh. The 16-electron biscarbene complexes [Ni(SPh)2{NHC}2] were isolated when an excess of HSPh was added to the reaction mixture. Biscarbene complexes of the type [NiBr2(NHC)2] were obtained in the reaction of NiCp2 with a slight excess of the specific imidazolium bromide salt. The molecular and electronic structures of the mono- and bis-N-heterocyclic carbene complexes have been analysed using single crystal diffraction and density functional theory (DFT) calculations, to give insight into their structural properties.

A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

Science.gov (United States)

Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2016-05-11

At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

Complexation of the cesium cation with 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6

Czech Academy of Sciences Publication Activity Database

Makrlík, E.; Dybal, Jiří; Vaňura, P.

2013-01-01

Roč. 295, č. 2 (2013), s. 1299-1303 ISSN 0236-5731 R&D Projects: GA ČR GA203/09/1478 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : cesium cation * substituted calix[4]arene-crown-6 * complexation Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.415, year: 2013

Experimental and DFT study on the complexation of the silver cation with calix[4]arene-bis(t-octylbenzo-18-crown-6)

International Nuclear Information System (INIS)

Makrlik, E.; Toman, P.; Vanura, P.

2013-01-01

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ag + (aq) + 1 x Cs + (org) ⇔ 1 x Ag + (org) + Cs + (aq) taking place in the two-phase water-phenyltrifluoromethyl sulfone (FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logK ex (Ag + , 1 x Cs + ) = -1.5 ± 0.1. Further, the stability constant of the 1 x Ag + complex in FS 13 saturated with water was calculated for a temperature of 25 deg C: log β org(1 x Ag + ) = 10.1 ± 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1 x Ag + was derived. In the resulting 1 x Ag + complex, the 'central' cation Ag + is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation-π interaction. (author)

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.

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

Science.gov (United States)

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

2015-07-27

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

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.

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.

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)

Electrochemistry of chromium(0)-aminocarbene complexes

International Nuclear Information System (INIS)

Hoskovcova, Irena; Rohacova, Jana; Meca, Ludek; Tobrman, Tomas; Dvorak, Dalimil; Ludvik, Jiri

2005-01-01

Two series of chromium(0)-(aryl)aminocarbene complexes substituted on the ligand phenyl ring were prepared and electrochemically investigated: pentacarbonyl((N,N-dimethylamino)(phenyl)carbene(chromium(0) (Ia-e) and chelated tetracarbonyl((η 2 -N-allyl-N-allylamino)(phenyl)carbene(chromium(0) (IIa, c-e). For comparison, a tungsten analogue of IIc (III) and a chromium chelate bearing a methyl substituent instead of the phenyl group IV were taken into the study. The intramolecular interactions of p-substituents on the ligand phenyl ring with the reduction and oxidation centres of the molecule of complex (followed electrochemically using LFER [P. Zuman, Substituent Effects in Organic Polarography, Plenum Press, New York, 1967]) enabled to localize the corresponding electron transfer. The influence of the type of coordination, the substituent on the ligand phenyl ring and the central metal atom on oxidation and reduction potentials is discussed

Characterization of the lanthanum(III) and europium(III) trichloroacetate complexes extracted with 18-crown-6

International Nuclear Information System (INIS)

Imura, H.; Saito, Y.; Ohashi, K.; Meguro, Y.; Yoshida, Z.; Choppin, G.R.

1996-01-01

Extraction of lanthanide(III) ions with 18-crown-6 (18C6) and trichloroacetate (tca) has been studied. The composition, hydration, and structure of the La(III) and Eu(III) complexes extracted into 1,2-dichloroethane were investigated by using several methods such as the liquid-liquid distribution technique, conductimetry, Karl Fisher titration, laser luminescence spectroscopy, and 1 H NMR. The La(III) complex was found to be a monohydrate, La(tca) 3 (18C6)(H 2 O), while that of Eu(III) was a mixture of a monohydrate and a dihydrate, i.e., Eu(tca) 3 (18C6)(H 2 O) and Eu(tca) 3 (18C6)(H 2 O) 2 . The origin of the selectivity by 18C6 which gives much higher extractability of La(III) than of Eu(III) is explained by considering the hydration and probable structure of their complexes. 12 refs., 5 figs., 4 tabs

Study of Sr sup 2+ and Eu sup 2+ complexing with 18-crown-6 in aqueous-ethanolic solutions. Izuchenie kompleksoobrazovaniya Sr sup 2+ i Eu sup 2+ s 18-kraun-6 v vodno-ehtanol'nykh rastvorakh

Energy Technology Data Exchange (ETDEWEB)

Kulyukhin, S A; Majorov, A V; Kamenskaya, A N; Mikheev, N B

1989-01-01

Using cocrystallization and conductometry methods Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 in aqueous-ethanolic solutions at (H{sub 2}O)=10 mol/l is studied. Stability constants of Sr{sup 2+} and Eu{sup 2+} complexes with 18-crown-6 in C{sub 2}H{sub 5}OH, for which lg{beta} is equal to (4.76{plus minus}0.12) and (4.72{plus minus}0.13) respectively, are determined. Comparison of the investigated elements features during complexing with 18-crown-6 in aqueous and aqueous-ethanolic solutions is carried out. It is shown that both in water and in C{sub 2}H{sub 5}OH -10 mol/l H{sub 2}O system under Sr{sup 2+} and Eu{sup 2+} complexing with 18-crown-6 the differences in properties of these elements are not detected.

Synthesis, structure, and properties of supramolecular charge-transfer complexes between bis(18-crown-6)stilbene and ammonioalkyl derivatives of 4,4'-bipyridine and 2,7-diazapyrene.

Science.gov (United States)

Vedernikov, Artem I; Ushakov, Evgeny N; Efremova, Asya A; Kuz'mina, Lyudmila G; Moiseeva, Anna A; Lobova, Natalia A; Churakov, Andrei V; Strelenko, Yuri A; Alfimov, Michael V; Howard, Judith A K; Gromov, Sergey P

2011-08-19

4,4'-Bipyridine and 2,7-diazapyrene derivatives (A) having two ammonioalkyl N-substituents were synthesized. The complex formation of these compounds with bis(18-crown-6)stilbene (D) was studied by spectrophotometry, cyclic voltammetry, (1)H NMR spectroscopy, and X-ray diffraction analysis. In MeCN, π-donor D and π-acceptors A form supramolecular 1:1 (D·A) and 2:1 (D·A·D) charge-transfer complexes. The D·A complexes have a pseudocyclic structure as a result of ditopic binding of the ammonium groups to the crown-ether fragments. The better the geometric matching between the components, the higher the stability of the D·A complexes (log K up to 9.39). A key driving force of the D·A·D complex formation is the excessive steric strain in the precursor D·A complexes. The pseudocyclic D·A complexes involving the ammoniopropyl derivative of 4,4'-bipyridine were obtained as single crystals. Crystallization of the related ammonioethyl derivative was accompanied by transition of the D·A complexes to a structure of the (D·A)(m) coordination polymer type.

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.

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

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

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.

Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

Science.gov (United States)

Song, Yingying; Cheng, Chen; Jing, Huanwang

2014-09-26

Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unusual centrosymmetric structure of [M(18-crown-6)](+) (M = Rb, Cs and NH4) complexes stabilized in an environment of hexachloridoantimonate(V) anions.

Science.gov (United States)

Ponomarova, Vira V; Rusanova, Julia A; Rusanov, Eduard B; Domasevitch, Konstantin V

2015-10-01

In (1,4,7,10,13,16-hexaoxacyclooctadecane)rubidium hexachloridoantimonate(V), [Rb(C12H24O6)][SbCl6], (1), and its isomorphous caesium {(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium hexachloridoantimonate(V), [Cs(C12H24O6)][SbCl6]}, (2), and ammonium {ammonium hexachloridoantimonate(V)-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1), (NH4)[SbCl6]·C12H24O6}, (3), analogues, the hexachloridoantimonate(V) anions and 18-crown-6 molecules reside across -3 axes passing through the Sb atoms and the centroids of the 18-crown-6 groups, both of which coincide with centres of inversion. The Rb(+) [in (1)], Cs(+) [in (2)] and NH4(+) [in (3)] cations are situated inside the cavity of the 18-crown-6 ring; they are situated on -3 axes and are equally disordered about centres of inversion, deviating from the centroid of the 18-crown-6 molecule by 0.4808 (13), 0.9344 (7) and 0.515 (8) Å, respectively. Interaction of the ammonium cation and the 18-crown-6 group is supported by three equivalent hydrogen bonds [N...O = 2.928 (3) Å and N-H...O = 162°]. The centrosymmetric structure of [Cs(18-crown-6)](+), with the large Cs(+) cation approaching the centre of the ligand cavity, is unprecedented and accompanied by unusually short Cs-O bonds [2.939 (2) and 3.091 (2) Å]. For all three compounds, the [M(18-crown-6)](+) cations and [SbCl6](-) anions afford linear stacks along the c axis, with the cationic complexes embedded between pairs of inversion-related anions.

Transcriptomic and anatomical complexity of primary, seminal, and crown roots highlight root type-specific functional diversity in maize (Zea mays L.).

Science.gov (United States)

Tai, Huanhuan; Lu, Xin; Opitz, Nina; Marcon, Caroline; Paschold, Anja; Lithio, Andrew; Nettleton, Dan; Hochholdinger, Frank

2016-02-01

Maize develops a complex root system composed of embryonic and post-embryonic roots. Spatio-temporal differences in the formation of these root types imply specific functions during maize development. A comparative transcriptomic study of embryonic primary and seminal, and post-embryonic crown roots of the maize inbred line B73 by RNA sequencing along with anatomical studies were conducted early in development. Seminal roots displayed unique anatomical features, whereas the organization of primary and crown roots was similar. For instance, seminal roots displayed fewer cortical cell files and their stele contained more meta-xylem vessels. Global expression profiling revealed diverse patterns of gene activity across all root types and highlighted the unique transcriptome of seminal roots. While functions in cell remodeling and cell wall formation were prominent in primary and crown roots, stress-related genes and transcriptional regulators were over-represented in seminal roots, suggesting functional specialization of the different root types. Dynamic expression of lignin biosynthesis genes and histochemical staining suggested diversification of cell wall lignification among the three root types. Our findings highlight a cost-efficient anatomical structure and a unique expression profile of seminal roots of the maize inbred line B73 different from primary and crown roots. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Silver(I) complexes of mono- and bidentate N-heterocyclic carbene ligands: synthesis, crystal structures, and in vitro antibacterial and anticancer studies.

Science.gov (United States)

Haque, Rosenani A; Choo, Sze Yii; Budagumpi, Srinivasa; Iqbal, Muhammad Adnan; Al-Ashraf Abdullah, Amirul

2015-01-27

A series of benzimidazole-based N-heterocyclic carbene (NHC) proligands {1-benzyl-3-(2-methylbenzyl)-benzimidazolium bromide/hexafluorophosphate (1/4), 1,3-bis(2-methylbenzyl)-benzimidazolium bromide/hexafluorophosphate (2/5) and 1,3-bis(3-(2-methylbenzyl)-benzimidazolium-1-ylmethylbenzene dibromide/dihexafluorophosphate (3/6)} has been synthesized by the successive N-alkylation method. Ag complexes {1-benzyl-3-(2-methylbenzyl)-benzimidazol-2-ylidenesilver(I) hexafluorophosphate (7), 1,3-bis(2-methylbenzyl)-benzimidazol-2-ylidenesilver(I) hexafluorophosphate (8) and 1,3-bis(3-(2-methylbenzyl)-benzimidazol-2-ylidene)-1-ylmethylbenzene disilver(I) dihexafluorophosphate (9)} of NHC ligands have been synthesized by the treatment of benzimidazolium salts with Ag2O at mild reaction conditions. Both, NHC proligands and Ag-NHC complexes have been characterized by (1)H and (13)C{(1)H} NMR and FTIR spectroscopy and elemental analysis technique. Additionally, the structure of the NHC proligand 5 and the mononuclear Ag complexes 7 and 8 has been elucidated by the single crystal X-ray diffraction analysis. Both the complexes exhibit the same general structural motif with linear coordination geometry around the Ag centre having two NHC ligands. Preliminary in vitro antibacterial potentials of reported compounds against a Gram negative (Escherichia coli) and a Gram positive (Bacillus subtilis) bacteria evidenced the higher activity of mononuclear silver(I) complexes. The anticancer studies against the human derived colorectal cancer (HCT 116) and colorectal adenocarcinoma (HT29) cell lines using the MTT assay method, revealed the higher activity of Ag-NHC complexes. The benzimidazolium salts 4-6 and Ag-NHC complexes 7-9 displayed the following IC50 values against the HCT 116 and HT29 cell lines, respectively, 31.8 ± 1.9, 15.2 ± 1.5, 4.8 ± 0.6, 10.5 ± 1.0, 18.7 ± 1.6, 1.20 ± 0.3 and 245.0 ± 4.6, 8.7 ± 0.8, 146.1 ± 3.1, 7.6 ± 0.7, 5.5 ± 0.8, 103.0 ± 2.3 μM. Copyright �

Crown ether complexes of lanthanoid and actinoid elements. Crystal and molecular structure of Nd(NO/sub 3/)/sub 3/(18-crown-6)

Energy Technology Data Exchange (ETDEWEB)

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

1980-01-01

Nd(NO/sub 3/)/sub 3/.18-Crown-6 crystallizes in the orthorhombic system, space group Pbca with eight molecules in a cell of dimensions a = 15.512(9), b = 21.662(1), c = 12.141(6) A. The structure has been determined by Patterson heavy-atom methods and refined by full-matrix least squares to R = 0.038. The neodymium atom is coordinated by 6 oxygen atoms of the 18-crown-6 unit and by three bidentate nitrate groups; one on the more hindered side of the ring and two on the opposite side.

Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

KAUST Repository

Collado, Alba; Balogh, Já nos; Meiries, Sé bastien; Slawin, Alexandra M. Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

2013-01-01

The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

KAUST Repository

Collado, Alba

2013-06-10

The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

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...

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

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.

Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids

OpenAIRE

Miller, Alexander J. M.; Labinger, Jay A.; Bercaw, John E.

2008-01-01

Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C−C bond has been formed between two reduced CO ligands. This prod...

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).

Complexes carbéniques nucléophiles de l'uranium

OpenAIRE

Tourneux , Jean-Christophe

2012-01-01

The only stable f-metal carbene complexes (excluding NHC) metals f present R2C(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 dianion C{Ph2P(=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...

Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

KAUST Repository

Sipos, Gellé rt; Ou, Arnold; Skelton, Brian W.; Falivene, Laura; Cavallo, Luigi; Dorta, Reto

2016-01-01

N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

KAUST Repository

Sipos, Gellért

2016-04-10

N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

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.

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.

Formation of methane versus benzene in the reactions of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) yielding thorium-carbene or thorium-ylide complexes

Energy Technology Data Exchange (ETDEWEB)

Rungthanaphatsophon, Pokpong; Behrle, Andrew C.; Barnes, Charles L.; Walensky, Justin R. [Department of Chemistry, University of Missouri, Columbia, MO (United States); Bathelier, Adrien; Castro, Ludovic; Maron, Laurent [Toulouse Univ. and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO (France)

2017-10-09

The reaction of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with the phosphonium salts [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C{sub 5}Me{sub 5}){sub 2}Th[CHPPh{sub 3}]X, rare terminal phosphorano-stabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds (∼2.30 Aa) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C{sub 5}Me{sub 5}){sub 2}Th[κ{sup 2}-(C,C{sup '})-(CH{sub 2})(CH{sub 2})PPh{sub 2}]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH{sub 3}PPh{sub 3}]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3

Directory of Open Access Journals (Sweden)

Felix S. Geitner

2017-07-01

Full Text Available We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene compounds of the germanium-rich metalloid clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3. NHCDippCu{η3Ge9R3} with R = Si(iPr3 (1 represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(iBu3 or Si(TMS3. The coordination of the [NHCDippCu]+ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge9] cluster. Furthermore, a series of novel Zintl cluster coinage metal NHC compounds of the type (NHCM2{η3Ge9RI2} (RI = Si(TMS3 M = Cu, Ag and Au; NHC = NHCDipp or NHCMes is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12Ge17 with Si(TMS3Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au, or via a homogenous reaction using the preformed bis-silylated cluster K2[Ge9(Si(TMS32] and the corresponding NHCMCl (M = Cu, Ag, Au complex. The molecular structures of NHCDippCu{η3Ge9(Si(iPr33} (1 and (NHCDippCu2{η3-Ge9(Si(TMS32} (2 were determined by single crystal X-ray diffraction methods. In 2, the coordination of the [NHCDippCu]+ moieties to the cluster unit takes place via both open triangular faces of the [Ge9] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (1H, 13C, 29Si and ESI-MS.

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.

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.

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.

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

Conductometric study of reaction kinetics between potassium superoxide and 18-crown-6 in dimethylsulfoxide

International Nuclear Information System (INIS)

Efimova, I.V.; Opejda, I.A.

2000-01-01

Complexing within KO 2 -18-crown-6-solvent, KOH-18-crown-6-solvent and KI-KO 2 -18-crown-6-solvent systems in dimethylsulfoxide was studied by measurement of electrical conductivity. It was shown that time variation of electrical conductivity under the given conditions was described by the Erofeev-Auramy equation, the coefficients of that equation for various systems were determined, time to reach equilibrium state was estimated. Linear dependences of electrical conductivity of KI-KO 2 salt solutions at presence of 18-crown-6 at the state of equilibrium in contrast to the component concentrations were determined [ru

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

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...

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.

Influence of the composition of aqueous dimethylsulfoxide solvent on thermodynamics of complexing between 18-crown-6-ether and D,L-alanine

Science.gov (United States)

Usacheva, T. R.; Kuzmina, I. A.; Sharnin, V. A.; Chernov, I. V.; Matteoli, E.

2012-07-01

Standard thermodynamic parameters (log K o, Δr H o, TΔr S o) of complexing 18-crown-6 ether (18C6) with D,L-alanine (Ala) in mixed water-dimethysulfoxide (H2O-DMSO) solvents are calculated on the basis of calorimetric titration results. A rise in the DMSO concentration in mixed solvent is found to increase stability and increase the exothermicity of the formation of [Ala-18C6] molecular complex. Changes in the reaction energetic are shown to be determined by changes in the solvation state of 18C6 that is the characteristic of the reactions of molecular complex formation between 18C6 and D,L-alanine or glycine in water-organic solvents.

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.

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.

First report of Fusarium redolens causing crown rot of wheat (Triticum spp.) in Turkey

Science.gov (United States)

Fusarium crown rot, caused by a complex of Fusarium spp., is a yield-limiting disease of wheat world-wide, especially in dry Mediterranean climates. In order to identify Fusarium species associated with crown rot of wheat, a survey was conducted in summer 2013 in the major wheat growing regions of T...

Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

KAUST Repository

Despagnet-Ayoub, Emmanuelle

2013-05-24

Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

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

Separation of americium (III) and strontium (II) using TEHDGA and 18-crown-6

Energy Technology Data Exchange (ETDEWEB)

Sinharoy, Prithwish; Khan, Pasupati Nath; Nair, Deepika; Jagasia, Poonam; Dhami, P.S.; Kaushik, C.P.; Banerjee, Kalyan [Bhabha Atomic Research Centre, Mumbai (India). Nuclear Recycle Group; Anitha, M. [Bhabha Atomic Research Centre, Mumbai (India). Rare Earth Development Section; Sharma, J.N. [Bhabha Atomic Research Centre, Mumbai (India). Process Development Div.

2017-06-01

This work describes extraction of Am(III) and Sr(II) together with tetra(2-ethylhexyl) diglycolamide (TEHDGA) and selective back-extraction of strontium with a strontium complexant, 18-crown-6, leading to their separation from each other. 0.3 M TEHDGA+5% isodecyl alcohol/n-dodecane was used to extract Am(III) and Sr(II) from 4 M nitric acid into organic phase with very high D (D{sub Am}=1000, D{sub Sr}=22) and 0.1 M 18-crown-6 dissolved in 4 M nitric acid is used for selective stripping of Sr(II) from loaded extract phase. Am(III) left in the extract phase was then stripped with 0.01 M nitric acid. Stripping of Sr(II) was found to increase with increase in 18-crown-6 concentration, at 0.1 M 18-crown-6 dissolved in 4 M nitric acid, 83% of the loaded strontium (D{sub Sr}=0.20) was back-extracted in a single contact while loss of Am(III) was 0.8% (D{sub Am}=122.45). Stoichiometry limit of 1:1 was observed between strontium and 18-crown-6. Strontium was precipitated and separated from the complexant by Na{sub 2}SO{sub 4} or Na{sub 2}CO{sub 3}. This process was tested with simulated solution of high level waste and found suitable for quantitative recovery of strontium with high purity.

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.

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.

Thermodynamics of formation for the 18-crown-6-triglycine molecular complex in water-dimethylsulfoxide solvents

Science.gov (United States)

Usacheva, T. R.; Lan, Pham Thi; Sharnin, V. A.

2014-06-01

The effect of a water-dimethylsulfoxide (DMSO) solvent on the formation of a molecular complex of 18-crown-6 (18C6) with triglycine (diglycylglycine, 3Gly) is studied via calorimetric titration. It is found that switching from water to an H2O-DMSO mixture with DMSO mole fraction of 0.30 is accompanied by a monotonic increase in the stability of [3Gly18C6] complex, from log K ∘ = 1.10 to log K ∘ = 2.44, and an increase in the exothermicity of the reaction of its formation, from -5.9 to -16.9 kJ/mol. It is shown that the [3Gly18C6] complex exhibits enthalpy stabilization with negative values of enthalpy and entropy over the investigated range of H2O-DMSO solvents. Analysis of the reagents' solvation characteristics reveals that the increase in the reaction's exothermicity of transfer is due to differences in the solvation of [3Gly18C6] and 18C6 with a small solvation contribution from 3Gly. It is concluded that the change in the Gibbs energy of the reaction 3Glysolv + 18C6solv ↔ [3Gly18C6]solv is due to differences in the change in the solvation state of the complex and the peptide (Δtr G ∘([3Gly18C6])-Δtr G ∘(3Gly)).

Versatility of {l_brace}M(30-crown-10){r_brace} (M = K{sup +}, Ba{sup 2+}) as a guest in UO{sub 2}{sup 2+} complexes of 3.1.3.1 - and 3.3.3 homo-oxa-calixarenes

Energy Technology Data Exchange (ETDEWEB)

Masci, B. [Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, (Italy); Thuery, P. [CEA Saclay, DSM/DRECAM/SCM, CNRS-URA 331, F-91191 Gif Sur Yvette, (France)

2007-07-01

The reaction between p-R-[3.1.3.1]- or [3.3.3] homo-oxa-calixarenes and uranyl salts in the presence of 30-crown-10 and the alkali or alkaline-earth metal cations K{sup +} or Ba{sup 2+} gives various supramolecular assemblages characterized by 'complex-within-complex' architectures. These can be of the simple nesting or sandwich types, as in [{l_brace}Ba(30-crown-10){r_brace}{l_brace}UO{sub 2}(L{sup 1}){r_brace}]. 2H{sub 2}O.3CHCl{sub 3} (L{sup 1}H{sub 4} p-tert-butyl[3.1.3.1] homo-oxa-calixarene) and [{l_brace}Ba(30-crown-10){r_brace}{l_brace}UO{sub 2}(L{sup 4}){r_brace}{sub 2}].2CHCl{sub 3} (L{sup 4}H{sub 3} p-bromo[3.3.3]homo-oxa-calixarene), respectively, with the cation held in the cavity of the homo-oxa-calixarene complexes in cone conformation by weak interactions, but more original structures arise when uranyl-cation bonds are present. In [{l_brace}Ba(30-crown-10){r_brace}{l_brace}UO{sub 2}(L{sup 2}){r_brace}] (L{sup 2}H{sub 4} p-phenyl[3.1.3.1] homo-oxa-calixarene), the barium ion included in the crown ether is bound to the uranyl oxo group located out of the calixarene cavity, resulting in the formation of a neutral species which self-organizes to form a columnar assembly by auto-inclusion. In [{l_brace}K(30-crown-10){r_brace}{l_brace}UO{sub 2}K(L{sup 1})(H{sub 2}O){sub 3}{r_brace}]{sub 2}.6H{sub 2}O, the nesting-type subunit dimerizes around two oxo-bound potassium ions. Finally, the use of the coordinating solvent dimethylsulfoxide leads to the neutral complex [UO{sub 2}Ba(L{sup 3})(dmso){sub 2}(MeOH)]{sub 2} (L{sup 3}H{sub 4} = p-methyl[3.1.3.1] homo-oxa-calixarene), in which the crown ether is absent and two oxo-, phenoxo- and ether-bound barium atoms ensure the dimerization of the uranyl complex. (authors)

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.

Reductive coupling of carbon monoxide in a rhenium carbonyl complex with pendant Lewis acids.

Science.gov (United States)

Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

2008-09-10

Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C-C bond has been formed between two reduced CO ligands. This product of C-C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.

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 ...

Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

KAUST Repository

Benhamou, Laure

2014-01-13

PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

KAUST Repository

Benhamou, Laure; Besnard, Cé line; Kü ndig, E. Peter

2014-01-01

PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

Study on complex formation of dicyclohexyl-18-crown-6 with Mg2+, Ca2+ and Sr2+ in acetonitrile-water binary mixtures by conductometry

OpenAIRE

Mallika Sanyal

2017-01-01

The complexation reactions between Mg2+, Ca2+ and Sr2+ cations and dicyclohexyl-18-crown-6 (DCH 18C6) have been studied in acetonitrile–water binary mixtures at different temperatures by conductometry. The formation constants of the resulting 1:1 (M:L) complexes for all the three cations were determined from computer fitting of the molar conductance versus mole ratio data. The results show that the selectivity order of DCH 18C6 for the metal cations in the acetonitrile-water binary solvent at...

Thermal transformations of oxohalide complexes of rhenium(5) and molybdenum(5) with diazo-18-crown-6 in solid phase

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.

1992-01-01

Methods for synthesis and separation in solid state of the rhenium(5) and molybdenum(5) onium complexes with diaza-18-crown-6(L), the content of which according to the data of elementary analysis, IRS in the close and remote areas, thermogravimetry, conductometry and potentiometry corresponds to the (H 2 L)[EOX 5 ], where E = Re, Mo; X = Cl - , Br - . Thermotransformation of onium compounds is studied by methods of thermal methods (TG-DTG-DTA combined study). Their avility to be affected by solid-phase dehydrohalogenization, e.i. anderson regrouping. The thermolysis products, corresponding to the general formula (EOLX 3 ), are separated and studied

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

Thin films of molecular materials synthesized from fisher's carbene ferrocenyl: Film formation and electrical properties

International Nuclear Information System (INIS)

Sanchez-Vergara, M.E.; Ortiz, A.; Alvarez-Toledano, C.; Moreno, A.; Alvarez, J.R.

2008-01-01

The synthesis of materials from Fisher's carbene ferrocenyl of the elements chromium, molybdenum and tungsten was carried out. The Fisher's compounds that were synthesized included the following combinations of two different metallic atoms: iron with chromium, iron with molybdenum and iron with tungsten. The molecular solids' preparation was done in electro-synthesis cells with platinum electrodes. Thin films were prepared by vacuum thermal evaporation on quartz substrates and crystalline silicon wafers. Pellets and thin films from these compounds were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy, atomic force microscopy and ellipsometry. The powder and thin films synthesized from these materials show the same intra-molecular bonds shown by infrared spectroscopy results, suggesting that thermal evaporation does not alter these bonds in spite of the thin films being amorphous, in contrast with other bimetallic complexes where material decomposition occurs. The differences in the conductivity values of the prepared films are very small, so they may be attributed to the different metallic ions employed in each case. The tungsten complex exhibits a higher conductivity than the molybdenum and chromium complexes at room temperature. Electrical conductivity values found for thin films are higher than for pellets made of the same molecular materials

Study of solvent effects on the stability constant and ionic mobility of the dibenzo-18-crown-6 complex with potassium ion by affinity capillary electrophoresis

Czech Academy of Sciences Publication Activity Database

Konášová, Renáta; Jaklová Dytrtová, Jana; Kašička, Václav

2016-01-01

Roč. 39, č. 22 (2016), s. 4429-4438 ISSN 1615-9306 R&D Projects: GA ČR(CZ) GA15-01948S; GA ČR GP13-21409P Institutional support: RVO:61388963 Keywords : affinity capillary electrophoresis * crown ethers * hydro-organic solvents * ionic mobility * potassium complexes Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 2.557, year: 2016

Biocontrol with Trichoderma species for the management of postharvest crown rot of banana

Directory of Open Access Journals (Sweden)

G. Sangeetha

2009-09-01

Full Text Available Lasiodiplodia theobromae and Colletotrichum musae cause the postharvest crown rot disease complex of banana. In vitro experiments evaluated the effect of twelve isolates of Trichoderma spp. from the soil of organic banana orchards (‘native isolates’ and eight isolates of Trichoderma spp. from culture collections (‘introduced isolates’ on the two pathogens. The native and introduced Trichoderma spp. had varied antagonistic effects against the two pathogens. Eight Trichoderma spp. isolates effective in the in vitro assays were evaluated singly on fruits both at room temperature and in cold storage. Single antagonists did not satisfactorily control crown rot on the fruits as compared with the fungicide carbendazim. However, two isolates of T. viride, one of T. harzianum and one of T. koningii performed well when applied singly, and these were selected for evaluation in isolate mixtures. There was very little antagonism between these isolates. Of 11 two-way, three-way and four-way mixtures of these isolates, the four-way and a three-way mixtures reduced crown rot incidence, both at room temperature and in cold storage, giving better control than carbendazim. The study identified consortia of compatible Trichoderma antagonists with superior biocontrol potential for the management of the postharvest crown rot complex of banana.

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

Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

KAUST Repository

Pump, Eva

2015-11-09

A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans

Management of complicated crown-root fracture in central incisors using intentional replantation with 180° rotation: A case report

Directory of Open Access Journals (Sweden)

Reyhaneh Faghihian

2017-01-01

Full Text Available Introduction: Complicated crown-root fractures are rare and their treatment is complex. Numerous methods such as crown lengthening and orthodontic or surgical extrusion have been described for the treatment of crown-root fracture. The aim of this study was to report managing complicated crown-root fracture using intentional replantation with 180° rotation. Case report: This case report demonstrates successful management of complicated crown-root fracture in central incisor of a 10-year-old boy using intentional replantation with 180° rotation. Discussion: At 18-month follow-up, the replanted tooth revealed normal function with no obvious resorption.

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.

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...

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.

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.

Supporting Information Palladium Complexes of a New Type of N ...

Indian Academy of Sciences (India)

Prasenjit Ghosh

Palladium Complexes of a New Type of N-heterocyclic Carbene. Ligand Derived From a Tricyclic Triazolooxazine Framework. Manoj Kumar Gangwar, Alok Ch. Kalita and Prasenjit Ghosh*. Department of Chemistry,. Indian Institute of Technology Bombay, ... 2. Figure S1. 1. H NMR spectrum of the compound 1a in CDCl3.

[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.

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

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

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.

18F-fluorination by crown ether-metal fluoride

International Nuclear Information System (INIS)

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

1982-01-01

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

Direct composite restoration of permanent anterior teeth uncomplicated crown fractures

Directory of Open Access Journals (Sweden)

Ashley Evans Nicholas

2018-01-01

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

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

International Nuclear Information System (INIS)

Dozol, M.

1990-01-01

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

Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

KAUST Repository

Nolan, Steven Patrick; Izquierdo, Frederic; Zinser, Caroline; Minenkov, Yury; Cordes, David; Slawin, Alexandra; Cavallo, Luigi; Nahra, Fady; Cazin, Catherine

2017-01-01

The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After

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)

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...

Theoretical Predictions of Redox Potentials of Fischer-Type Chromium Anninocarbene Complexes

Czech Academy of Sciences Publication Activity Database

Kvapilová, Hana; Hoskovcová, Irena; Ludvík, Jiří; Záliš, Stanislav

2014-01-01

Roč. 33, č. 18 (2014), s. 4964-4972 ISSN 0276-7333 R&D Projects: GA MŠk LD14129; GA ČR GA13-04630S Institutional support: RVO:61388955 Keywords : standard hydrogen electrode * density functional theory * metal carbene complexes Subject RIV: CG - Electrochemistry Impact factor: 4.126, year: 2014

Crown structure, radiation absorption, photosynthesis and transpiration

OpenAIRE

Wang, Yingping

1988-01-01

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

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…

Crystal structure of cis-anti-cis-dicyclohexane-18-crown-6 acetonitrile disolvate

Directory of Open Access Journals (Sweden)

Alexander Nazarenko

2015-07-01

Full Text Available The title compound (systematic name: cis-anti-cis-2,5,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosane acetonitrile disolvate, C20H36O6·2CH3CN, crystallizes from an acetonitrile solution of dicyclohexane-18-crown-6 on evaporation. The molecule is arranged around a center of symmetry with half the crown ether molecule and one molecule of acetonitrile symmetry independent. All O—C—C—O torsion angles are gauche while all C—O—C—C angles are trans. The sequence of torsion angles is [(tg+t(tg−t]3; the geometry of oxygen atoms is close to pseudo-D3d with three atoms below and three atoms above the mean plane, with an average deviation of ±0.16 (1 Å from the mean plane. This geometry is identical to that observed in metal ion complexes of dicyclohexane-18-crown-6 but differs significantly from the conformation of a free unsolvated molecule. Each acetonitrile molecule connects to a crown ether molecule via two of its methyl group H atoms (C—H...O. Weaker interactions exist between the third H atom of the acetonitrile methyl group and an O atom of a neighbouring crown ether molecule (C—H...O; and between the N atom of the acetonitrile molecule and a H atom of another neighbouring crown ether molecule. All these intermolecular interactions create a three-dimensional network stabilizing the disolvate.

Rhenium (5) and molybdenum (5) complexes with 4',4''(5'')-ditretbutyldibenzo-24-crown-8. Kompleksnye soedineniya reniya (5) i molibdena (5) s 4',4''(5'')-ditretbutildibenzo-24-kraun-8

Energy Technology Data Exchange (ETDEWEB)

Ashurova, N Kh; Yakubov, K G; Basitova, S M; Tashmukhamedova, A K; Sajfullina, N Zh [Tadzhikskij Gosudarstvennyj Univ., Dushanbe (USSR)

1989-10-01

Rhenium and molybdenum complexes in +5 oxidation degree with 4',4''(5'')-ditretbutyldibenzo-24-crown-8 (L) are synthesized with 75-95 % yield. Composition and structure of compounds produced are investigated using element analysis, conductometry, IR spectroscopy, thermogravimetry methods. Oxidation degree of complexer metal is determined. It is ascertained that the compound composition corresponds to the MOLX{sub 3} formula, where M-Re, Mo; X-Cl{sup -}, Br{sup -}.

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.

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.

Reversed phase partition chromatographic separation of Gd(III) on poly(Crown Ether) column

International Nuclear Information System (INIS)

Mahanwar, K.R.; Sabale, S.R.

2014-01-01

A simple method has been developed for the separation of Gd(III) in hippuric acid medium by using poly(dibenzo-18-crown-6) as stationary phase. The effect of hippuric acid concentration, different eluting agent, foreign ions etc was studied and the optimum conditions were established. Breakthrough capacity of poly(dibenzo-18-crown-6) for Gd(III) was found to be 0.572 ±0.01 mmolg -1 of crown polymer. The separation of Gd(III) from other elements in multicomponent mixtures has been achieved. The method was extended for determination of Gd(III) in real sample. The method is simple, rapid and selective with good reproducibility (approximately ± 2%). Crown ethers are widely used as complexing agent that can selectively capture metal cation in their cavity. This special feature shown by poly (dibenzo-18-crown-6) has been used in our laboratory for selective cation exchanger by column chromatography. No attempts were made for the separation of Gd(III) using hippuric acid media and column chromatography. The present communication describes a simple and sensitive method for the determination of Gd(III) using poly(dibenzo-18-crown-6) as stationary phase in hippuric acid medium. The proposed method affords an attractive feature as compared to the solvent extraction technique i.e. it is free from any organic diluents as an environmental concern

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

Directory of Open Access Journals (Sweden)

Carmen Mejuto

2015-12-01

Full Text Available The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene complex with three [IrCl(CO2] fragments, allowed the estimation of the Tolman electronic parameter (TEP for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

Synthesis, characterization and sup 23 Na NMR shift studies of a novel dysprosium(III) crown ether texaphyrin

Energy Technology Data Exchange (ETDEWEB)

Sessler, J.L.; Mody, T.D. (Texas Univ., Austin, TX (United States). Dept. of Chemistry); Ramasamy, R.; Sherry, A.D. (Texas Univ., Dallas, TX (United States))

1992-05-01

The synthesis and characterization of a novel dysprosium(III) crown-ether texaphyrin (Dy(BCTxp)){sup 2+} is reported. This complex was designed to serve as a ditopic chelate for both dysprosium(III) and sodium cations. {sup 23}Sodium NMR spectroscopic studies indicates that titration of Na{sup +} with increasing concentrations of (Dy(BCTxp)){sup 2+} results in a shift toward higher frequency and gives a net hyperfine shift of 0.86 ppm. Sodium complexation is taking place into the crown subunit in (Dy(BCTxp)){sup 2+} and the degree of complexation is not reduced substantially by the positive charge on the dysprosium(III) portion of this binucleating system.

Evaluation of various Crown ethers for the supercritical fluid extraction of uranium from nitric acid medium

International Nuclear Information System (INIS)

Kumar, Pradeep; Rao, Ankita; Ramakumar, K.L.

2009-01-01

Various crowns have been evaluated for supercritical fluid extraction of uranium from nitric acid medium employing HPFOA as counter ion. Uranium extraction efficiency was found to be influenced by cavity size of crown ether and nature of substituents. Complexation tendency of UO 2 2+ increases with increasing cavity size of crown ether. Electron withdrawing substituents decreased the extraction efficiency which could be attributed to decrease in the basicity of four oxygen atoms and hence their bonding ability. Whereas electron donating substituents increased the efficiency due to increases in basicity of oxygen atoms and hence in increase in bonding ability. (author)

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....

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.

M(0) - Aminocarbene complexes (M = Cr, W, Fe): Redox Behavior Tuned by Metal and/or ligand modification

Czech Academy of Sciences Publication Activity Database

Hoskovcová, I.; Roháčová, J.; Dvořák, D.; Ludvík, Jiří

2006-01-01

Roč. 2, č. 23 (2006), s. 87-95 ISSN 1938-5862 R&D Projects: GA ČR GA203/04/0487 Institutional research plan: CEZ:AV0Z40400503 Keywords : carbene complexes * electrochemistry Subject RIV: CG - Electrochemistry

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.

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.

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.

Thin films of molecular materials synthesized from fisher's carbene ferrocenyl: Film formation and electrical properties

Energy Technology Data Exchange (ETDEWEB)

Sanchez-Vergara, M.E. [Coordinacion de Ingenieria Mecatronica. Escuela de Ingenieria, Universidad Anahuac del Norte. Avenida Lomas de la Anahuac s/n, Col. Lomas Anahuac, 52786, Huixquilucan (Mexico)], E-mail: elena.sanchez@anahuac.mx; Ortiz, A. [Instituto de Investigaciones en Materiales. Universidad Nacional Autonoma de Mexico. A. P. 70-360, 04510, Mexico, DF (Mexico); Alvarez-Toledano, C.; Moreno, A. [Instituto de Quimica, Universidad Nacional Autonoma de Mexico. Circuito Exterior, Ciudad Universitaria, 04510, Mexico, DF (Mexico); Alvarez, J.R. [Instituto Tecnologico y de Estudios Superiores de Monterrey, Campus Ciudad de Mexico. Calle del Puente 222, Col. Ejidos de Huipulco, 14380, Mexico, DF (Mexico)

2008-07-31

The synthesis of materials from Fisher's carbene ferrocenyl of the elements chromium, molybdenum and tungsten was carried out. The Fisher's compounds that were synthesized included the following combinations of two different metallic atoms: iron with chromium, iron with molybdenum and iron with tungsten. The molecular solids' preparation was done in electro-synthesis cells with platinum electrodes. Thin films were prepared by vacuum thermal evaporation on quartz substrates and crystalline silicon wafers. Pellets and thin films from these compounds were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy, atomic force microscopy and ellipsometry. The powder and thin films synthesized from these materials show the same intra-molecular bonds shown by infrared spectroscopy results, suggesting that thermal evaporation does not alter these bonds in spite of the thin films being amorphous, in contrast with other bimetallic complexes where material decomposition occurs. The differences in the conductivity values of the prepared films are very small, so they may be attributed to the different metallic ions employed in each case. The tungsten complex exhibits a higher conductivity than the molybdenum and chromium complexes at room temperature. Electrical conductivity values found for thin films are higher than for pellets made of the same molecular materials.

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.

2ΔH(D) and 1ΔN(D) isotope effects on nuclear shielding of ammonium ions in complexes with crown ethers and cryptands

International Nuclear Information System (INIS)

Hansen, P.E.; Hansen, Aa.E.; Lycka, A.; Buvari-Barcza, A.

1993-01-01

One-bond deuterium isotope effects on nitrogen nuclear shielding, 1 ΔN(D) and two-bond isotope effects at 1 H nuclear shielding, 2 ΔH(D), have been investigated in a series of inclusion complexes. The hosts comprise, SC-24, [2.2.2], [2.2.1], [2.2.1] D, [2.2] DD, K5, 18-crown-6 and 18-crown-6 tetracarboxylic acid. The structure of the host [2.2.1] is discussed based on isotope effects and 1 H chemical shifts, and an interesting exchange reaction is observed between CDCl 3 and ammonium ions in the [2.2.1] complex. The counterion dependence is shown to be zero for ammonium ions fully included in cages such as SC-24 and [2.2.2] and for 18-C-6(COOH) 4 . For cryptands and podands such as [2.2.1] and K5 a weak counterion dependence of 2 ΔH(D) opposite to that found for ammonium ions in water is observed, while 1 ΔN(D) and 15 N chemical shifts depend very strongly on the counterions, as also found for ammonium ions in water solution. The anilinium ion shows effects similar to those observed for the ammonium ion. 1 ΔN(D) isotope effects correlate well with δN and 2 ΔH(D) correlate with δNH. The correlation between 1 ΔN(D) and 2 ΔH(D) is different for ammonium ions in water and ions included in crowns, cryptands or podands. This shows that different mechanisms are operating. The 2 ΔH(D) isotope effects and δNH chemical shifts depend on the distance to the nearest acceptor (oxygen or nitrogen), and they also depend on the type of acceptor. 2 ΔH(D) isotope effects are found to be a good gauge of N ... N or N ... O distances of the inclusion complexes. The 2 ΔH(D) isotope effects vary with temperature, but the dramatic changes in the 1 H NMR spectra of the host are not reflected in the isotope effects. The one-bond couplings, 1 J(N,H), correlate with 2 ΔH(D). The variations are much larger for the cryptands than found in water solutions. (au) (50 refs.)

Crown ether complexes of actinide elements. An X-ray study of the conformational change of the crown ether within the UO/sub 2/(NO/sub 3/)/sub 2/(H/sub 2/O)/sub 2/(18-crown-6) molecule

Energy Technology Data Exchange (ETDEWEB)

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

1978-01-01

Uranyl nitrate dihydrate-18-crown-6 crystallizes in the triclinic system with a = 9.072(3), b = 9.144(3), c = 8.323(3) A; ..cap alpha.. = 64.53(10)/sup 0/, ..beta.. = 104.23(10)/sup 0/, ..gamma.. = 110.72(10)/sup 0/, space group P1. Its structure has been determined from three dimensional X-ray data collected with an automatic diffractometer at room temperature and refined with full matrix methods to the final conventional R value = 0.038. The uranyl group does not enter into the 18-crown-6 cavity, but presents the usual hexacoordination in the equatorial plane where two water molecules and the bidentate nitrato groups are coordinated trans to each other. The whole structure is constituted by neutral UO/sub 2/(NO/sub 3/)/sub 2/(H/sub 2/O)/sub 2/ units alternated with 18-crown-6 molecules and linked together in infinite chains developing along (001) through a hydrogen bonding system. The cyclic ether assumes two statistically non-equivalent sites in the crystal (occupancy factor 0.7 and 0.3 respectively) related to each other by a 180/sup 0/ rotation about 0(7)...0(7') axis.

EXTRACTION OF STRONTIUM(II BY CROWN ETHER: INSIGHTS FROM DENSITY FUNCTIONAL CALCULATION

Directory of Open Access Journals (Sweden)

Saprizal Hadisaputra

2012-12-01

Full Text Available The structures, energetic and thermodynamic parameters of crown ethers with different cavity size, electron donating/withdrawing substituent groups and donor atoms have been determined with density functional method at B3LYP level of theory in gas and solvent phase. Small core quasi-relativistic effective core potentials was used together with the accompanying SDD basis set for Sr2+ and DZP basis set was used for crown ether atoms. Natural bond orbital (NBO analysis was evaluated to characterize the distribution of electrons on the complexes. The interaction energy is well correlated with the values of Strontium charge after complexation, the second order interaction energies (E2 and HOMO-LUMO energy gab (∆Egab. The interaction energy and thermodynamics parameters in gas phase are reduced in solvent phase as the solvent molecules weaken the metal-crown ether interaction. The thermodynamic parameters indicated that less feasibility to extract Sr2+ ion directly from pure water without presence of organic solvent. The theoretical values of extraction energy for Sr(NO32 salt from aqueous solution in different organic solvent is validated by the experimental trend. This study would have strong contribution in planning the experiments to the design of specific host ligand and screening of solvent for extraction of metal ion.

Synthesis, Structure and Catalytic Activity of NHC-AgICarboxylate Complexes

KAUST Repository

Wong, Valerie H. L.; Vummaleti, Sai V. C.; Cavallo, Luigi; White, Andrew J. P.; Nolan, Steven P.; Hii, King Kuok Mimi

2016-01-01

A general synthetic route was used to prepare 15 new N-heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand-accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Synthesis, Structure and Catalytic Activity of NHC-AgICarboxylate Complexes

KAUST Repository

Wong, Valerie H. L.

2016-08-03

A general synthetic route was used to prepare 15 new N-heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand-accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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

Synthesis of New Chiral Benzimidazolylidene–Rh Complexes and Their Application in Asymmetric Addition Reactions of Organoboronic Acids to Aldehydes

Directory of Open Access Journals (Sweden)

Weiping He

2016-09-01

Full Text Available A series of novel chiral N-heterocyclic carbene rhodium complexes (NHC–Rh based on benzimidazole have been prepared, and all of the NHC–Rh complexes were fully characterized by NMR and mass spectrometry. These complexes could be used as catalysts for the asymmetric 1,2-addition of organoboronic acids to aldehydes, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

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 ...

MULTISEASONAL TREE CROWN STRUCTURE MAPPING WITH POINT CLOUDS FROM OTS QUADROCOPTER SYSTEMS

Directory of Open Access Journals (Sweden)

S. Hese

2017-08-01

Full Text Available OTF (Off The Shelf quadro copter systems provide a cost effective (below 2000 Euro, flexible and mobile platform for high resolution point cloud mapping. Various studies showed the full potential of these small and flexible platforms. Especially in very tight and complex 3D environments the automatic obstacle avoidance, low copter weight, long flight times and precise maneuvering are important advantages of these small OTS systems in comparison with larger octocopter systems. This study examines the potential of the DJI Phantom 4 pro series and the Phantom 3A series for within-stand and forest tree crown 3D point cloud mapping using both within stand oblique imaging in different altitude levels and data captured from a nadir perspective. On a test site in Brandenburg/Germany a beach crown was selected and measured with 3 different altitude levels in Point Of Interest (POI mode with oblique data capturing and deriving one nadir mosaic created with 85/85 % overlap using Drone Deploy automatic mapping software. Three different flight campaigns were performed, one in September 2016 (leaf-on, one in March 2017 (leaf-off and one in May 2017 (leaf-on to derive point clouds from different crown structure and phenological situations – covering the leaf-on and leafoff status of the tree crown. After height correction, the point clouds where used with GPS geo referencing to calculate voxel based densities on 50 × 10 × 10 cm voxel definitions using a topological network of chessboard image objects in 0,5 m height steps in an object based image processing environment. Comparison between leaf-off and leaf-on status was done on volume pixel definitions comparing the attributed point densities per volume and plotting the resulting values as a function of distance to the crown center. In the leaf-off status SFM (structure from motion algorithms clearly identified the central stem and also secondary branch systems. While the penetration into the

Multiseasonal Tree Crown Structure Mapping with Point Clouds from OTS Quadrocopter Systems

Science.gov (United States)

Hese, S.; Behrendt, F.

2017-08-01

OTF (Off The Shelf) quadro copter systems provide a cost effective (below 2000 Euro), flexible and mobile platform for high resolution point cloud mapping. Various studies showed the full potential of these small and flexible platforms. Especially in very tight and complex 3D environments the automatic obstacle avoidance, low copter weight, long flight times and precise maneuvering are important advantages of these small OTS systems in comparison with larger octocopter systems. This study examines the potential of the DJI Phantom 4 pro series and the Phantom 3A series for within-stand and forest tree crown 3D point cloud mapping using both within stand oblique imaging in different altitude levels and data captured from a nadir perspective. On a test site in Brandenburg/Germany a beach crown was selected and measured with 3 different altitude levels in Point Of Interest (POI) mode with oblique data capturing and deriving one nadir mosaic created with 85/85 % overlap using Drone Deploy automatic mapping software. Three different flight campaigns were performed, one in September 2016 (leaf-on), one in March 2017 (leaf-off) and one in May 2017 (leaf-on) to derive point clouds from different crown structure and phenological situations - covering the leaf-on and leafoff status of the tree crown. After height correction, the point clouds where used with GPS geo referencing to calculate voxel based densities on 50 × 10 × 10 cm voxel definitions using a topological network of chessboard image objects in 0,5 m height steps in an object based image processing environment. Comparison between leaf-off and leaf-on status was done on volume pixel definitions comparing the attributed point densities per volume and plotting the resulting values as a function of distance to the crown center. In the leaf-off status SFM (structure from motion) algorithms clearly identified the central stem and also secondary branch systems. While the penetration into the crown

Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

KAUST Repository

Anneser, Markus R.; Haslinger, Stefan; Pö thig, Alexander; Cokoja, Mirza; D'Elia, Valerio; Hö gerl, Manuel P.; Basset, Jean-Marie; Kü hn, Fritz E.

2016-01-01

The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure

Toward engineering intra-receptor interactions into bis(crown ethers).

Science.gov (United States)

Krause, Martin R; Kubik, Stefan

2012-03-01

A synthetic receptor was designed in which cooperative binding of two crown ether moieties to an alkali metal ion simultaneously causes two hydrophobic substituents not involved in direct host-guest interactions to converge. Hydrophobic interactions between these substituents can be expected to contribute to the overall complex stability. Independent binding studies involving two diastereoisomers of this bis(crown ether), one in which intra-receptor interactions between the substituents are potentially possible and one in which they are not, using isothermal titration calorimetry showed that both isomers bind potassium ions in different solvent mixtures with the same overall affinity. Profound differences were observed for each isomer, however, in the enthalpies and entropies of binding, which are consistent with intra-receptor interactions in one compound. These interactions are counteracted by enthalpy-entropy compensation so that no overall improvement in cation affinity could be observed.

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.

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers.

Science.gov (United States)

Du, H S; Wood, D J; Elshani, S; Wai, C M

1993-02-01

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.

Esthetic rehabilitation of complicated crown fractures utilizing rapid orthodontic extrusion and two different restoration modalities.

Science.gov (United States)

Milardovic Ortolan, Sladana; Strujic, Mihovil; Aurer, Andrej; Viskic, Josko; Bergman, Lana; Mehulic, Ketij

2012-01-01

This case report describes the management of a crown-root fractured maxillary right central incisor and a crown fractured maxillary left central incisor using two different techniques. A complex procedure was designed to manage this case including orthodontic extrusion to move the fracture line above the alveolar bone and surgical recontouring of the altered gingival margin. Finally, the right incisor was restored prosthodontically. Prosthetic treatment was based on performing a post and core, and all-ceramic crown on the extruded tooth. The left, less-damaged incisor was restored directly using composite resin. The treatment resulted in good esthetics and secured periodontal health. This case report demonstrates that a multidisciplinary treatment approach is a reliable and predictable option to save a tooth. How to cite this article: Ortolan SM, Strujic M, Aurer A, Viskic J, Bergman L, Mehulic K. Esthetic Rehabilitation of Complicated Crown Fractures Utilizing Rapid Orthodontic Extrusion and Two Different Restoration Modalities. Int J Clin Pediatr Dent 2012;5(1):64-67.

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.

Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

Science.gov (United States)

Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

2015-05-11

A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tree crown structural characterization: A study using terrestrial laser scanning and three-dimensional radiative transfer modeling

Science.gov (United States)

Moorthy, Inian

Spectroscopic observational data for vegetated environments, have been coupled with 3D physically-based radiative transfer models for retrievals of biochemical and biophysical indicators of vegetation health and condition. With the recent introduction of Terrestrial Laser Scanning (TLS) units, there now exists a means of rapidly measuring intricate structural details of vegetation canopies, which can also serve as input into 3D radiative transfer models. In this investigation, Intelligent Laser Ranging and Imaging System (ILRIS-3D) data was acquired of individual tree crowns in laboratory, and field-based experiments. The ILRIS-3D uses the Time-Of-Flight (TOF) principle to measure the distances of objects based on the time interval between laser pulse exitance and return, upon reflection from an object. At the laboratory-level, this exploratory study demonstrated and validated innovative approaches for retrieving crown-level estimates of Leaf Area Index (LAI) (r2 = 0.98, rmse = 0.26m2/m2), a critical biophysical parameter for vegetation monitoring and modeling. These methods were implemented and expanded in field experiments conducted in olive (Olea europaea L.) orchards in Cordoba, Spain, where ILRIS-3D observations for 24 structurally-variable trees were made. Robust methodologies were developed to characterize diagnostic architectural parameters, such as tree height (r2 = 0.97, rmse = 0.21m), crown width (r 2 = 0.98, rmse = 0.12m), crown height (r2 = 0.81, rmse = 0.11m), crown volume (r2 = 0.99, rmse = 2.6m3), and LAI (r2 = 0.76, rmse = 0.27m2/ m2). These parameters were subsequently used as direct inputs into the Forest LIGHT (FLIGHT) 3D ray tracing model for characterization of the spectral behavior of the olive crowns. Comparisons between FLIGHT-simulated spectra and measured data showed small differences in the visible (measurements were significantly correlated to TLS-derived tree crown complexity metrics. The specific implications of internal crown

Modeling tree crown dynamics with 3D partial differential equations.

Science.gov (United States)

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

2014-01-01

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

Solvent mimicry with methylene carbene to probe protein topography.

Science.gov (United States)

Gómez, Gabriela Elena; Monti, José Luis E; Mundo, Mariana Rocío; Delfino, José María

2015-10-06

The solvent accessible surface area (SASA) of the polypeptide chain plays a key role in protein folding, conformational change, and interaction. This fundamental biophysical parameter is elusive in experimental measurement. Our approach to this problem relies on the reaction of the minimal photochemical reagent diazirine (DZN) with polypeptides. This reagent (i) exerts solvent mimicry because its size is comparable to water and (ii) shows scant chemical selectivity because it generates extremely reactive methylene carbene. Methylation gives rise to the EM (extent of modification) signal, which is useful for scrutinizing the conformational change triggered by Ca(2+) binding to calmodulin (CaM). The increased EM observed for the full protein is dominated by the enhanced exposure of hydrophobic area in Ca(2+)-CaM. Fragmentation allowed us to quantify the methylene incorporation at specific sites. Peptide 91-106 reveals a major reorganization around the calcium 151 binding site, resulting in local ordering and a greater exposure of the hydrophobic surface. Additionally, this technique shows a high sensitivity to probe recognition between CaM and melittin (Mel). The large decrease in EM indicates the occlusion of a significant hydrophobic area upon complexation. Protection from labeling reveals a larger involvement of the N-terminal and central regions of CaM in this interaction. Despite its smaller size, Mel's differential exposure can also be quantified. Moreover, MS/MS fragmentation realizes the goal of extending the resolution of labeled sites at the amino acid level. Overall, DZN labeling emerges as a useful footprinting method capable of shedding light on physiological conformational changes and interactions.

Electronic Excitations in Fischer-Type Cr and W Aminocarbene Complexes: A Combined ab Initio and Experimental Study

Czech Academy of Sciences Publication Activity Database

Kvapilová, Hana; Hoskovcová, Irena; Kayanuma, M.; Daniel, CH.; Záliš, Stanislav

2013-01-01

Roč. 117, č. 45 (2013), s. 11456-11463 ISSN 1089-5639 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : METAL CARBENE COMPLEXES * FLASH-PHOTOLYSIS * BASIS-SETS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.775, year: 2013

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.

Exciplex emission and photoinduced energy transfer as a function of cavity dimension in naphthalene-linked aza-crown ethers

International Nuclear Information System (INIS)

Roy, Mailrayee Basu; Samanta, Subhodip; Chattopadhyay, Gautam; Ghosh, Sanjib

2004-01-01

We report here the photophysical properties of two derivatives of N-(β-methylnaphthalene) aza-crown systems having different cavity dimensions. The aza-crown moiety is attached to β-position of naphthalene moiety by one >CH 2 unit in both the derivatives. The cavity size is found to have a pronounced effect on exciplex formation as well as energy transfer in the systems at room temperature and low temperature, respectively. Both the systems exhibit photoinduced electron transfer (PET) which is evident from their weaker fluorescence emission and their quenched singlet lifetimes as compared to that of free naphthalene. The systems also show a solvent sensitive red shifted broad structureless emission which is assigned to exciplex formation. The ratio of quantum yields of exciplex to monomer emission (phi (cursive,open) Greek Exp /phi (cursive,open) Greek M ) is lower in the smaller aza-crown (L1) as compared to that in the larger aza-crown (L2) implying a different geometry of the two systems in the excited state. Semi-emperical calculations performed on the systems also corroborate the different geometry of the two systems. Complexation of alkali metals, rare earth ions and protons by the aza-crown moiety results in enhancement of fluorescence emission due to blocking of PET. In the presence of protons, L1 exhibits a new emission due to excimer formation which has not been observed in L2 under similar conditions. The rare earth ion complexes of L1 and L2 at low temperature exhibit energy transfer from the lowest triplet state of naphthalene to the rare earth ion states, the extent of energy transfer being greater in the larger aza-crown (L2) as compared to that in smaller aza-crown system (L1)

Olefin Metathesis with Ru-Based Catalysts Exchanging the Typical N-Heterocyclic Carbenes by a Phosphine–Phosphonium Ylide

Directory of Open Access Journals (Sweden)

Laia Arnedo

2017-03-01

Full Text Available Density functional theory (DFT calculations have been used to describe the first turnover of an olefin metathesis reaction calling for a new in silico family of homogenous Ru-based catalysts bearing a phosphine–phosphonium ylide ligand, with ethylene as a substrate. Equal to conventional Ru-based catalysts bearing an N-heterocyclic carbene (NHC ligand, the activation of these congeners occurs through a dissociative mechanism, with a more exothermic first phosphine dissociation step. In spite of a stronger electron-donating ability of a phosphonium ylide C-ligand with respect to a diaminocarbene analogue, upper energy barriers were calculated to be on average ca. 5 kcal/mol higher than those of Ru–NHC standards. Overall, the study also highlights advantages of bidentate ligands over classical monodentate NHC and phosphine ligands, with a particular preference for the cis attack of the olefin. The new generation of catalysts is constituted by cationic complexes potentially soluble in water, to be compared with the typical neutral Ru–NHC ones.

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

Separation and determination of a trace amount of lithium as its thenoyltrifluoroacetone complex with 12-crown-4 by means of synergic extraction and flame photometry

OpenAIRE

Itoh, Tatsuo; Billah, Mokarram; Honjo, Takaharu; Terada, Kikuo

1991-01-01

A new method for the separation and determination of a trace amount of lithium in ppb∼ppm level in water as its thenoyltrifluoroacetone (TTA) complex with 12-crown-4 (12C4) has been established by means of synergic extraction and back extraction combined with flame photometry. The effect of various factors (pH, solvent, reagent concentration, shaking time, preconcentration factor, and foreign ions etc.) on the extraction and back extraction of lithium has been investigated. Here the lithium T...

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers

International Nuclear Information System (INIS)

Du, H.S.; Wood, D.J.; Elshani, Sadik; Wai, C.M.

1993-01-01

Thorium and the lanthanides are extracted by α-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed. (author)

Stability complexes of lanthanide ions with some macrocyclic polyethers

International Nuclear Information System (INIS)

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

1984-01-01

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

Evaluating crown fire rate of spread predictions from physics-based models

Science.gov (United States)

C. M. Hoffman; J. Ziegler; J. Canfield; R. R. Linn; W. Mell; C. H. Sieg; F. Pimont

2015-01-01

Modeling the behavior of crown fires is challenging due to the complex set of coupled processes that drive the characteristics of a spreading wildfire and the large range of spatial and temporal scales over which these processes occur. Detailed physics-based modeling approaches such as FIRETEC and the Wildland Urban Interface Fire Dynamics Simulator (WFDS) simulate...

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

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.

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

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...

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.

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. 

Antibacterial and DNA cleavage activity of carbonyl functionalized N-heterocyclic carbene-silver(I) and selenium compounds

Science.gov (United States)

Haque, Rosenani A.; Iqbal, Muhammad Adnan; Mohamad, Faisal; Razali, Mohd R.

2018-03-01

The article describes syntheses and characterizations of carbonyl functionalized benzimidazolium salts, I-IV. While salts I-III are unstable at room temperature, salt IV remained stable and was further utilised to form N-heterocyclic carbene (NHC) compounds of silver(I), V and VI, and selenium compound, VII respectively. Compounds IV-VII were tested for their antibacterial potential against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Salt IV shows a very low inhibition potential (minimum inhibitory concentration, MIC 500 μg/mL) compared to the respective silver(I)-NHC, V and VI (MIC 31.25 μg/mL against both, E. coli and S. aureus) and selenium compound, VII (MIC 125 μg/mL against E. coli and 62.50 μg/mL against S. aureus). In DNA cleavage abilities, all the test compounds cleave DNA in which the VII cleaves the DNA at the faster rate. Meanwhile, the silver(I)-NHC complexes V and VI act at the same mode and pattern of DNA cleavage while VII is similar to IV.

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

Directory of Open Access Journals (Sweden)

André Knoesen

2012-05-01

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

In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

Science.gov (United States)

Pinaud, Julien; Trinh, Thi Kim Hoang; Sauvanier, David; Placet, Emeline; Songsee, Sriprapai; Lacroix-Desmazes, Patrick; Becht, Jean-Michel; Tarablsi, Bassam; Lalevée, Jacques; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

2018-01-09

1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 - ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl 2 (p-cymene)] 2 precatalyst, the highly active RuCl 2 (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature. To the best of our knowledge, this is the first example of a photogenerated NHC. Its exploitation in photoROMP has resulted in a simplified process compared to current photocatalysts, because only stable commercial or easily synthesized reagents are required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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...

Fungi associated with fruit crown rot in organic banana (Musa spp. L. in Piura, Peru

Directory of Open Access Journals (Sweden)

René Aguilar Anccota

2013-05-01

Full Text Available The department of Piura is the principal banana-producing zone in Peru, sharing 87% of exportations. In this zone, one of the most important postharvest diseases is crown rot. The economic loses attributed to this disease are estimated to be between 25 and 30% of organic bananas exported. The objective of this study was to identify the causal agents associated with this disease. Samples taken refrigerated fruit from the areas of Querecotillo, Salitral and Mallares were taken and selected after the fact. Thielaviopsis paradoxa, Lasiodiplodia theobromae, Colletotrichum musae and Fusarium verticilloides. In order to demonstrate the pathogenicity of the isolated species, inoculations were given in the area of the crown of the fruit on healthy bananas. These fungi caused symptoms of infection in different proportions, concluding that crown rot is a disease with a complex etiology.

Selective crystallization of cations with crown ethers; Selektive Kristallisation von Kationen mit Kronenethern

Energy Technology Data Exchange (ETDEWEB)

Heffels, Dennis Egidius

2014-07-04

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

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

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...

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.

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...

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.

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...

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.

π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

KAUST Repository

Credendino, Raffaele

2012-05-16

In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

[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

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.

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

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.

Rhenium(5) and molybdenum(5) complexes with 4',4[sup (]5[sup )]-divaleryldibenzo-18-crown-6. Kompleksnye soedineniya reniya(5) i molibdena(5) s 4',4[sup (]5[sup )]-divalerildibenzo-18-kraun-6

Energy Technology Data Exchange (ETDEWEB)

Ashurova, N Kh; Yakubov, K G; Tashmukhamedova, A K; Basitova, S M [Tadzhikskij Gosudarstvennyj Univ., Dushanbe (Tajikistan)

1993-02-01

Methods for synthesizing oxohalide complexes of rhenium and molybdenum with +5 oxidation degree with 4',4[sup (5)]-divaleryldibenzo-18-crown-6 were developed. Content and composition of prepared compounds were investigated by the methods of element analysis, crystal optics, conductometry, IR spectroscopy in the near and far regions, thermogravimetry. Oxidation degree of the complex-forming metal was determined. It was established that composition of the compounds coressponded to the general formula MOLX [sub [center dot

Formation of cyclobutanones by the photolytic reaction of (CO)/sub 5/Cr/double bond/C(OMe)Me with electron-rich olefins

Energy Technology Data Exchange (ETDEWEB)

Sierra, M.A.; Hegedus, L.S.

1989-03-15

Recent research has centered on the development of useful organic synthetic methodology based on the photolytic reactions of chromium Fischer carbene complexes, particularly in regards to the development of new /beta/-lactam syntheses. In the course of these studies it became evident that photolysis of chromium-carbene complexes resulted in the reversible production of chromium-ketene complexes, by a photochemically driven CO insertion into the chromium-carbene carbon double bond and that this unstable intermediate was responsible for /beta/-lactam formation.

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....

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

International Nuclear Information System (INIS)

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

1975-01-01

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

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2016-01-01

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju

2016-04-13

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

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.

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.

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....

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').

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')

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.

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.

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.

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.

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

Science.gov (United States)

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

1998-08-01

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

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.

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...

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...

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

Unraveling the synthesis of homoleptic [Ag(N,N-diaryl-NHC)2]Y (Y = BF4, PF6) complexes by ball-milling.

Science.gov (United States)

Beillard, Audrey; Bantreil, Xavier; Métro, Thomas-Xavier; Martinez, Jean; Lamaty, Frédéric

2016-11-28

A user-friendly and general mechanochemical method was developed to access rarely described NHC (N-heterocyclic carbene) silver(i) complexes featuring N,N-diarylimidazol(idin)ene ligands and non-coordinating tetrafluoroborate or hexafluorophosphate counter anions. Comparison with syntheses in solution clearly demonstrated the superiority of the ball-milling conditions.

Enhanced π-Back-Donation as a Way to Higher Coordination Numbers in d10 [M(NHC)n] Complexes: A DFT Study

NARCIS (Netherlands)

Nitsch, J.; Wolters, L.P.; Fonseca Guerra, C.; Bickelhaupt, F.M.; Steffen, A.

2016-01-01

We aim to understand the electronic factors determining the stability and coordination number of d10 transition-metal complexes bearing N-heterocyclic carbene (NHC) ligands, with a particular emphasis on higher coordinated species. In this DFT study on the formation and bonding of Group 9–12 d10

Enhanced pi-Back-Donation as a Way to Higher Coordination Numbers in d10 [M(NHC)n] Complexes: A DFT Study

NARCIS (Netherlands)

Nitsch, J.S.; Wolters, L.P.; Fonseca Guerra, C.; Bickelhaupt, F.M.; Steffen, A.

2017-01-01

We aim to understand the electronic factors determining the stability and coordination number of d10 transition-metal complexes bearing N-heterocyclic carbene (NHC) ligands, with a particular emphasis on higher coordinated species. In this DFT study on the formation and bonding of Group 9–12 d10

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.

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.

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).

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.

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.

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.

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...

A 20-Year Overview of Quercus robur L. Mortality and Crown Conditions in Slovenia

Directory of Open Access Journals (Sweden)

Matjaž Čater

2015-02-01

Full Text Available Pedunculate oak (Quercus robur L. forests in Slovenia are experiencing widespread mortality. Changes in lowlands are reflected in decline of complete forest complexes, high mortality, uneven stand structure and associated forest regeneration problems. Prediction of the present-tree response in disturbed forest ecosystems may significantly contribute to better guideline policies for the silvicultural and forest management practice in the changing environment in both stressed and stabile forest ecosystems. Data from annual crown condition surveys for the 1995–2014 period from four permanent plots have been compared with parameters from hemispherical photo analysis and hydrometeorological data. Good agreement has been confirmed between crown defoliation and total openness; all parameters from the hemispherical photo analysis, which were corrected for winter period values, also indicated a better agreement. Mortality rate and crown defoliation correlated well with extreme drought events in 2003 and 2013. Pattern of agreement among compared parameters was different for the plots Krakovski gozd, Dobrava and some other plots. Mortality is influenced by the average air temperatures much more than by precipitation and groundwater table oscillations.

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...

Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

Science.gov (United States)

Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

2014-05-21

Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

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:

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.

[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.

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)

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)

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.

Synthesis, characterization and luminescence studies of gold(I–NHC amide complexes

Directory of Open Access Journals (Sweden)

Adrián Gómez-Suárez

2013-10-01

Full Text Available A flexible, efficient and straightforward methodology for the synthesis of N-heterocyclic carbene gold(I–amide complexes is reported. Reaction of the versatile building block [Au(OH(IPr] (1 (IPr = 1,3-bis(2,6-diisopropylphenylimidazol-2-ylidene with a series of commercially available (heteroaromatic amines leads to the synthesis of several [Au(NRR’(IPr] complexes in good yields and with water as the sole byproduct. Interestingly, these complexes present luminescence properties. UV–vis and fluorescence measurements have allowed the identification of their excitation and emission wavelengths (λmax. These studies revealed that by selecting the appropriate amine ligand the emission can be easily tuned to achieve a variety of colors, from violet to green.

[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.

Modelling fruit-temperature dynamics within apple tree crowns using virtual plants.

Science.gov (United States)

Saudreau, M; Marquier, A; Adam, B; Sinoquet, H

2011-10-01

Fruit temperature results from a complex system involving the climate, the tree architecture, the fruit location within the tree crown and the fruit thermal properties. Despite much theoretical and experimental evidence for large differences (up to 10 °C in sunny conditions) between fruit temperature and air temperature, fruit temperature is never used in horticultural studies. A way of modelling fruit-temperature dynamics from climate data is addressed in this work. The model is based upon three-dimensional virtual representation of apple trees and links three-dimensional virtual trees with a physical-based fruit-temperature dynamical model. The overall model was assessed by comparing model outputs to field measures of fruit-temperature dynamics. The model was able to simulate both the temperature dynamics at fruit scale, i.e. fruit-temperature gradients and departure from air temperature, and at the tree scale, i.e. the within-tree-crown variability in fruit temperature (average root mean square error value over fruits was 1·43 °C). This study shows that linking virtual plants with the modelling of the physical plant environment offers a relevant framework to address the modelling of fruit-temperature dynamics within a tree canopy. The proposed model offers opportunities for modelling effects of the within-crown architecture on fruit thermal responses in horticultural studies.

Effects of histidin-2-ylidene vs. imidazol-2-ylidene ligands on the anticancer and antivascular activity of complexes of ruthenium, iridium, platinum, and gold

Czech Academy of Sciences Publication Activity Database

Schmitt, F.; Donnelly, K.; Muenzner, J.K.; Rehm, T.; Novohradský, Vojtěch; Brabec, Viktor; Kašpárková, Jana; Albrecht, M.; Schobert, R.; Mueller, T.

2016-01-01

Roč. 163, OCT2016 (2016), s. 221-228 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GA14-21053S Institutional support: RVO:68081707 Keywords : n-heterocyclic carbene * human cancer-cells * metal-complexes Subject RIV: BO - Biophysics Impact factor: 3.348, year: 2016

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

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

Extraction of calcium from water into nitrobenzene using strontium dicarbollylcobaltate in the presence of 18-crown-6

Directory of Open Access Journals (Sweden)

EMANUEL MAKRLIK

2000-04-01

Full Text Available From extraction experiments and g-activity measurements, the extraction constant corresponding to the equilibrium Ca2+(aq + SrL2+(nb « CaL2+(nb + Sr2+(aq taking place in the two-phase water-nitrobenzene system (L = 18-crown-6, aq = aqueous phase, nb = nitrobenzene phase was evaluated as log Kex(Ca2+, SrL2+ = -1. 9±0.1. Furthermore, the stability constant of the calcium - 18-crown-6 complex in nitrobenzene saturated with water was calculated for the temperature of 25°C: log bnb (CaL2+ = 10.1±0.1.

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.

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-02-15

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

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.

Extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application for separating uranium and thorium

International Nuclear Information System (INIS)

Wang Wenji; Sun Quing; Chen Bozhong

1986-01-01

The extraction of uranium with dicyclohexano-18-crown-6 (mixed isomers) is described. The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Isub(a)) and isomer B (Isub(b)) in 1,2-dichloroethane is presented. The extracted species were found to be 1:2 (metal/crown) for Isub(a) and 2:3 for Isub(b) from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Ksub(ex)) were determined at 25 deg C and are equal to 29.5 and 0.208, respectively. It is concluded that Isub(a) has a stronger coordination ability for uranium than Isub(b). The different orientation of lone pairs of the oxygen atoms in both isomers has to be taken into account for interpereting the above results. (author)

A cerium(IV)-carbon multiple bond

Energy Technology Data Exchange (ETDEWEB)

Gregson, Matthew; Lu, Erli; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry

2013-12-02

Straightforward access to a cerium(IV)-carbene complex was provided by one-electron oxidation of an anionic ''ate'' cerium(III)-carbene precursor, thereby avoiding decomposition reactions that plague oxidations of neutral cerium(III) compounds. The cerium(IV)-carbene complex is the first lanthanide(IV)-element multiple bond and involves a twofold bonding interaction of two electron pairs between cerium and carbon. [German] Auf direktem Wege zu einem Cer(IV)-Carbenkomplex gelangt man durch die Einelektronenoxidation einer anionischen Carben-Cerat(III)-Vorstufe. So werden Zersetzungsprozesse vermieden, die die Oxidation neutraler Cer(III)-Verbindungen erschweren. Der Cer(IV)-Carbenkomplex enthaelt die erste Lanthanoid(IV)-Element-Mehrfachbindung; dabei binden Cer und Kohlenstoff ueber zwei Elektronenpaare.

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.

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.

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.

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...

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

International Nuclear Information System (INIS)

Guyon, Vincent

1992-01-01

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

Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

KAUST Repository

Veenboer, Richard M. P.

2017-09-08

The synthesis and isolation of gold(I) precatalysts often requires the generation of several isolable intermediates as well as numerous purification steps. New protocols for the expedient synthesis of neutral [Au(OH)(NHC)] and [Au(CH2COCH3)(NHC)] species from [AuCl(NHC)] or [AuCl(DMS)] precursors bearing a variety of N-heterocyclic carbene (NHC) ligands are presented. These methods can be employed in a telescoping manner for the synthesis of catalytically relevant [Au(NTf2)(NHC)] and [Au(NHC)(NCCH3)][BF4] complexes. These attractive methods are straightforward and practical leading to various complexes in high isolated yields and purity.

Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

KAUST Repository

Veenboer, Richard M. P.; Gasperini, Danila; Nahra, Fady; Cordes, David B.; Slawin, Alexandra M. Z.; Cazin, Catherine S. J.; Nolan, Steven P.

2017-01-01

The synthesis and isolation of gold(I) precatalysts often requires the generation of several isolable intermediates as well as numerous purification steps. New protocols for the expedient synthesis of neutral [Au(OH)(NHC)] and [Au(CH2COCH3)(NHC)] species from [AuCl(NHC)] or [AuCl(DMS)] precursors bearing a variety of N-heterocyclic carbene (NHC) ligands are presented. These methods can be employed in a telescoping manner for the synthesis of catalytically relevant [Au(NTf2)(NHC)] and [Au(NHC)(NCCH3)][BF4] complexes. These attractive methods are straightforward and practical leading to various complexes in high isolated yields and purity.

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.

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.

Extraction of lithium with nitrobenzene solution of strontium bis-1,2-dicarbollylcobaltate in the presence of 15-crown-5

International Nuclear Information System (INIS)

Makrlik, E.; Dankova, M.

1999-01-01

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium 2Li + (aq)+SrL 2 2+ (nb) ↔ 2LiL + (nb)+Sr 2+ (aq) taking place in the two-phase water-nitrobenzene system (L = 15-crown-5; aq = aqueous phase, nb nitrobenzene phase) was evaluated as log K ex (2Li + ;SrL 2 2+ ) = -3.7. Further, the stability constant of the 15-crown-5 - lithium complex in nitrobenzene saturated with water was calculated: log β nb (LiL + ) 7.0. (author)

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

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)

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.

Thermal transformations of oxohalide complexes of rhenium(5) and molybdenum(5) with diazo-18-crown-6 in solid phase. Termicheskie prevrashcheniya oksogalogenidnykh kompleksov reniya(5) i molibdena(5) s diaza-18-kraun-6 v tverdoj faze

Energy Technology Data Exchange (ETDEWEB)

Ashurova, N Kh; Yakubov, K G [Tadzhikskij Gosudarstvennyj Univ., Dushanbe (Tajikistan)

1992-11-01

Methods for synthesis and separation in solid state of the rhenium(5) and molybdenum(5) onium complexes with diaza-18-crown-6(L), the content of which according to the data of elementary analysis, IRS in the close and remote areas, thermogravimetry, conductometry and potentiometry corresponds to the (H[sub 2]L)[EOX[sub 5

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

[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.

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.

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...

Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

Energy Technology Data Exchange (ETDEWEB)

Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

2014-12-08

In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

Optimal Cluster Mill Pass Scheduling With an Accurate and Rapid New Strip Crown Model

International Nuclear Information System (INIS)

Malik, Arif S.; Grandhi, Ramana V.; Zipf, Mark E.

2007-01-01

Besides the requirement to roll coiled sheet at high levels of productivity, the optimal pass scheduling of cluster-type reversing cold mills presents the added challenge of assigning mill parameters that facilitate the best possible strip flatness. The pressures of intense global competition, and the requirements for increasingly thinner, higher quality specialty sheet products that are more difficult to roll, continue to force metal producers to commission innovative flatness-control technologies. This means that during the on-line computerized set-up of rolling mills, the mathematical model should not only determine the minimum total number of passes and maximum rolling speed, it should simultaneously optimize the pass-schedule so that desired flatness is assured, either by manual or automated means. In many cases today, however, on-line prediction of strip crown and corresponding flatness for the complex cluster-type rolling mills is typically addressed either by trial and error, by approximate deflection models for equivalent vertical roll-stacks, or by non-physical pattern recognition style models. The abundance of the aforementioned methods is largely due to the complexity of cluster-type mill configurations and the lack of deflection models with sufficient accuracy and speed for on-line use. Without adequate assignment of the pass-schedule set-up parameters, it may be difficult or impossible to achieve the required strip flatness. In this paper, we demonstrate optimization of cluster mill pass-schedules using a new accurate and rapid strip crown model. This pass-schedule optimization includes computations of the predicted strip thickness profile to validate mathematical constraints. In contrast to many of the existing methods for on-line prediction of strip crown and flatness on cluster mills, the demonstrated method requires minimal prior tuning and no extensive training with collected mill data. To rapidly and accurately solve the multi-contact problem

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 ...

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...

Photodissociative Cross-Linking of Non-covalent Peptide-Peptide Ion Complexes in the Gas Phase

Science.gov (United States)

Nguyen, Huong T. H.; Andrikopoulos, Prokopis C.; Rulíšek, Lubomír; Shaffer, Christopher J.; Tureček, František

2018-05-01

We report a gas-phase UV photodissociation study investigating non-covalent interactions between neutral hydrophobic pentapeptides and peptide ions incorporating a diazirine-tagged photoleucine residue. Phenylalanine (Phe) and proline (Pro) were chosen as the conformation-affecting residues that were incorporated into a small library of neutral pentapeptides. Gas-phase ion-molecule complexes of these peptides with photo-labeled pentapeptides were subjected to photodissociation. Selective photocleavage of the diazirine ring at 355 nm formed short-lived carbene intermediates that underwent cross-linking by insertion into H-X bonds of the target peptide. The cross-link positions were established from collision-induced dissociation tandem mass spectra (CID-MS3) providing sequence information on the covalent adducts. Effects of the amino acid residue (Pro or Phe) and its position in the target peptide sequence were evaluated. For proline-containing peptides, interactions resulting in covalent cross-links in these complexes became more prominent as proline was moved towards the C-terminus of the target peptide sequence. The photocross-linking yields of phenylalanine-containing peptides depended on the position of both phenylalanine and photoleucine. Density functional theory calculations were used to assign structures of low-energy conformers of the (GLPMG + GLL*LK + H)+ complex. Born-Oppenheimer molecular dynamics trajectory calculations were used to capture the thermal motion in the complexes within 100 ps and determine close contacts between the incipient carbene and the H-X bonds in the target peptide. This provided atomic-level resolution of potential cross-links that aided spectra interpretation and was in agreement with experimental data. [Figure not available: see fulltext.

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.

Ion pair recognition by Zn-porphyrin/crown ether conjugates: visible sensing of sodium cyanide.

Science.gov (United States)

Kim, Yeon-Hwan; Hong, Jong-In

2002-03-07

Synthesis and complexation behavior of ditopic neutral receptors composed of both a Lewis-acidic binding site (zinc porphyrin moiety) and a Lewis-basic binding site (crown ether moiety) are reported; the receptors bound only NaCN in a ditopic fashion with a color change, and in contrast other sodium salts bound to the receptors in a monotopic fashion without a color change.

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.

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

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

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...

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.

Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2.

Science.gov (United States)

Lalrempuia, Ralte; Breivik, Frida; Törnroos, Karl W; Le Roux, Erwan

2017-06-27

Tetravalent zirconium complexes supported by tridentate bis-phenolate imidazolidin-2-ylidene (L1), imidazol-2-ylidene (L2) and benzimidazol-2-ylidene (L3) NHC ligands were synthesized and evaluated as precursors for the copolymerization of cyclohexene oxide (CHO) with CO 2 . While the reactivity of the imidazolidinium [H 3 L1] chloride salt with Zr(OiPr) 4 (HOiPr), and subsequent ligand exchanges with either (CH 3 ) 3 SiCl or LiOiPr lead to a series of heteroleptic compounds (κ 3 -O,C,O-L1)Zr(X) 2 (THF) (X = Cl, OiPr), both imidazolium [H 3 L2] and benzimidazolium [H 3 L3] chloride salts give a mixture of homoleptic (κ 3 -O,C,O-NHC) 2 Zr and zwitterionic (κ 2 -O,O-HL)ZrCl 2 (OiPr) compounds along with traces or the absence of the heteroleptic intermediate (κ 3 -O,C,O-NHC)Zr(Cl)(OiPr)(THF). Such dissimilar reactivity between the unsaturated and saturated NHC ligands is predominantly ascribed to the increased acidity of azolium salts along with the π-donor strength of the C carbene in L2 and L3-Zr moieties. The reactivity with the more acidic azolium salts (H 3 L2/3) and the destabilized Zr-X trans to NHC carbene bond results in a significant increase in the amount of homoleptic compounds generating HCl. The released HCl reacts preferentially with the heteroleptic intermediates having non-planar NHC ligands (i.e. L2/3) promoting the formation of zwitterionic complexes. The in situ deprotonation of the isolated zwitterionic (κ 2 -O,O-HL3)ZrCl 2 (OiPr) compound by using Ag 2 O gives the homoleptic complex as the major component along with a bimetallic hydroxo-bridged [(κ 3 -O,C,O-L3)Zr(μ-OH)(OiPr)] 2 compound. Of particular interest is that only the heteroleptic NHC-Zr(iv) complexes were identified to be active and highly selective towards the copolymerization of CHO with CO 2 independently of the co-catalysts used (both anionic and neutral) under mild conditions (P CO 2 < 1 bar, T = 60 °C), and gave atactic and completely alternating copolymers in a

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.

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.

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

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)

Influence of micro-topography and crown characteristics on tree height estimations in tropical forests based on LiDAR canopy height models

Science.gov (United States)

Alexander, Cici; Korstjens, Amanda H.; Hill, Ross A.

2018-03-01

Tree or canopy height is an important attribute for carbon stock estimation, forest management and habitat quality assessment. Airborne Laser Scanning (ALS) based on Light Detection and Ranging (LiDAR) has advantages over other remote sensing techniques for describing the structure of forests. However, sloped terrain can be challenging for accurate estimation of tree locations and heights based on a Canopy Height Model (CHM) generated from ALS data; a CHM is a height-normalised Digital Surface Model (DSM) obtained by subtracting a Digital Terrain Model (DTM) from a DSM. On sloped terrain, points at the same elevation on a tree crown appear to increase in height in the downhill direction, based on the ground elevations at these points. A point will be incorrectly identified as the treetop by individual tree crown (ITC) recognition algorithms if its height is greater than that of the actual treetop in the CHM, which will be recorded as the tree height. In this study, the influence of terrain slope and crown characteristics on the detection of treetops and estimation of tree heights is assessed using ALS data in a tropical forest with complex terrain (i.e. micro-topography) and tree crown characteristics. Locations and heights of 11,442 trees based on a DSM are compared with those based on a CHM. The horizontal (DH) and vertical displacements (DV) increase with terrain slope (r = 0.47 and r = 0.54 respectively, p tree height are up to 16.6 m on slopes greater than 50° in our study area in Sumatra. The errors in locations (DH) and tree heights (DV) are modelled for trees with conical and spherical tree crowns. For a spherical tree crown, DH can be modelled as R sin θ, and DV as R (sec θ - 1). In this study, a model is developed for an idealised conical tree crown, DV = R (tan θ - tan ψ), where R is the crown radius, and θ and ψ are terrain and crown angles respectively. It is shown that errors occur only when terrain angle exceeds the crown angle, with the

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....

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 ...

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

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.

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.

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

Interaction between adrenaline and dibenzo-18-crown-6: Electrochemical, nuclear magnetic resonance, and theoretical study

Science.gov (United States)

Yu, Zhang-Yu; Liu, Tao; Wang, Xue-Liang

2014-12-01

The interaction between adrenaline (Ad) and dibenzo-18-crown-6 (DB18C6) was studied by cyclic voltammetry, nuclear magnetic resonance spectroscopy, and the theoretical calculations, respectively. The results show that DB18C6 will affect the electron transfer properties of Ad. DB18C6 can form stable supramolecular complexes with Ad through ion-dipole and hydrogen bond interactions.

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.

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 ...

Viscoelastic finite element analysis of residual stresses in porcelain-veneered zirconia dental crowns.

Science.gov (United States)

Kim, Jeongho; Dhital, Sukirti; Zhivago, Paul; Kaizer, Marina R; Zhang, Yu

2018-06-01

The main problem of porcelain-veneered zirconia (PVZ) dental restorations is chipping and delamination of veneering porcelain owing to the development of deleterious residual stresses during the cooling phase of veneer firing. The aim of this study is to elucidate the effects of cooling rate, thermal contraction coefficient and elastic modulus on residual stresses developed in PVZ dental crowns using viscoelastic finite element methods (VFEM). A three-dimensional VFEM model has been developed to predict residual stresses in PVZ structures using ABAQUS finite element software and user subroutines. First, the newly established model was validated with experimentally measured residual stress profiles using Vickers indentation on flat PVZ specimens. An excellent agreement between the model prediction and experimental data was found. Then, the model was used to predict residual stresses in more complex anatomically-correct crown systems. Two PVZ crown systems with different thermal contraction coefficients and porcelain moduli were studied: VM9/Y-TZP and LAVA/Y-TZP. A sequential dual-step finite element analysis was performed: heat transfer analysis and viscoelastic stress analysis. Controlled and bench convection cooling rates were simulated by applying different convective heat transfer coefficients 1.7E-5 W/mm 2 °C (controlled cooling) and 0.6E-4 W/mm 2 °C (bench cooling) on the crown surfaces exposed to the air. Rigorous viscoelastic finite element analysis revealed that controlled cooling results in lower maximum stresses in both veneer and core layers for the two PVZ systems relative to bench cooling. Better compatibility of thermal contraction coefficients between porcelain and zirconia and a lower porcelain modulus reduce residual stresses in both layers. Copyright © 2018 Elsevier Ltd. All rights reserved.

Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

KAUST Repository

Vummaleti, Sai V. C.; Falivene, Laura; Poater, Albert; Cavallo, Luigi

2014-01-01

We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

KAUST Repository

Vummaleti, Sai V. C.

2014-05-02

We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

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.

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.

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.

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.

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.

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

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.

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.

Chemistry of Iron N -heterocyclic carbene complexes: Syntheses, structures, reactivities, and catalytic applications

KAUST Repository

Riener, Korbinian

2014-05-28

Iron is the most abundant transition metal in Earth\\'s crust. It is relatively inexpensive, not very toxic, and environmentally benign. Undoubtedly, due to the involvement in a multitude of biological processes, which heavily rely on the rich functionalities of iron-containing enzymes, iron is one of the most important elements in nature. Additionally, three-coordinate iron complexes have been reported during the past several years. In this review, the mentioned iron NHC complexes are categorized by their main structure and reactivity attributes. Thus, monocarbene and bis-monocarbene complexes are presented first. This class is subdivided into carbonyl, nitrosyl, and halide compounds followed by a brief section on other, more unconventional iron NHC motifs. Subsequently, donor-substituted complexes bearing bi-, tri-, tetra-, or even pentadentate ligands and further pincer as well as scorpionato motifs are described.

Crown condition assessment at the CONECOFOR Permanent Monitoring Plots

Directory of Open Access Journals (Sweden)

Renzo NIBBI

2002-09-01

Full Text Available A detailed crown condition assessment is currently being carried out at the CONECOFOR (CONtrollo ECOsistemi FORestali, Control of Forest Ecosystems plots. The assessment began in 1996, and during the first two years (1996 and 1997 an assessment form based on previous regional experience was used; in 1998 the new official EU form was adopted. The resulting loss of comparability means that only a few indices can be used in the temporal series 1996-1999. Much effort was devoted to Quality Assurance (QA procedures. The QA program is structured as follows: (i specific field manuals have been adopted and are continuously updated; (ii a national training and intercalibration course (NT&IC is undertaken yearly before beginning the assessment campaign;( iii field checks are carried out yearly on a large number of plots. The results of the QA program have shown that for several indices the quality objectives were not reached, but the quality of the data is improving with time. To express the change in crown conditions in each area, a complex index (CCI = Crown Condition Index was adopted. This index is the result of the sum of the relativized values of all the common indices used during the four years. The following parameters were used: transparency, ramification type, leaf colour alteration extension, leaf damage extension, alteration of leaf distension extension. The range within which the CCI fluctuates was evaluated taking into account all the observations carried out at a given plot throughout the years. The number of cases over a given threshold (outliers was calculated for each year. The threshold for outliers was calculated as the median value plus 2 times the range of the interquartile value. All individual cases exceeding this value are considered outliers. The results are presented for all the areas in which the data set is complete for the four years. The yearly fluctuations are discussed and related to possible causes.

The principles for creation of fire-prevention forest belts with barriers of deciduous species for protection from crown fires