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.

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.

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

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

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)

Influence of structure of crown ethers on their radiation stability

International Nuclear Information System (INIS)

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

1988-01-01

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

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

Increasing the thermopower of crown-ether-bridged anthraquinones

Science.gov (United States)

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

2015-10-01

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

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.

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...

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.

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...

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.

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)

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)

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.

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.

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.

Effect of electrostatic interaction on thermochemical behavior of 12-crown-4 ether in various polar solvents

International Nuclear Information System (INIS)

Barannikov, Vladimir P.; Guseynov, Sabir S.; Vyugin, Anatoliy I.

2010-01-01

The enthalpies of solution of 12-crown-4 ether have been measured in chloroform, ethyl acetate, acetone, pyridine, acetonitrile and methanol at 298.15 K. The values of enthalpy of solvation and solute-solvent interaction were determined from the obtained results and similar literature data for 12-crown-4 in solvents of various polarities. It was shown that the certain correlation is observed between the enthalpy of solute-solvent interaction and the squared dipole moment of the solvent molecules for solutions in tetrachlormethane, ethyl acetate, pyridine, acetonitrile, DMF, DMSO and propylene carbonate. This means that the electrostatic interaction of 12-crown-4 with polar solvent molecules contributes significantly to the exothermic effect of solvation. The understated negative value was found for the enthalpy of interaction of 12-crown-4 with acetone that can be connected with domination of low polar conformer of the crown ether in acetone medium. The most negative values of enthalpy of solvation are observed for solutions in chloroform and water because of hydrogen bonding between O-atoms of crown ether and molecules of the indicated solvents. This effect is not observed for methanol. The negative coefficient of pairwise solute-solute interaction in methanol indicates that the effects of solvophobic solute-solute interaction and H-bonding of the ether molecule with chain associates of methanol are not evinced in the thermochemical behavior of 12-crown-4.

Polyacrylonitrile (PAN)/crown ether composite nanofibers for the selective adsorption of cations

NARCIS (Netherlands)

Tas, Sinem; Kaynan, Ozge; Ozden-Yenigun, Elif; Nijmeijer, Dorothea C.

2016-01-01

In this study, we prepared electrospun polyacrylonitrile (PAN) nanofibers functionalized with dibenzo-18-crown-6 (DB18C6) crown ether and showed the potential of these fibers for the selective recovery of K+ from other both mono- and divalent ions in aqueous solutions. Nanofibers were characterized

Gamma-radiolysis of benzosubstituted crown ethers

International Nuclear Information System (INIS)

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

1992-01-01

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

Functionalized mesoporous silicas with crown ether moieties for selective adsorption of lithium ions in artificial sea water.

Science.gov (United States)

Sung, Soo Park; Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang-Sik

2014-11-01

Lithium ion has been increasingly recognized in a wide range of industrial applications. In this work, we studied on the adsorption of Li+ in the artificial seawater with high selectivity using methyl-crown ether (AC-SBA-15) and aza-crown ether (HMC-SBA-15) moieties-functionalized mesoporous silica materials. First, methyl-crown ether and aza-crown ether moieties-functionalized mesoporous silica materials were synthesized via two-step post-synthesis process using a grafting method. The functionalized materials were employed to the metal ion adsorption from aqueous solution (artificial seawater) containing Li+, Co2+, Cr3+ and Hg2+. The prepared hybrid material showed high selectivity for Li+ ion in the artificial seawater at pH 8.0. The absorbed amount of Li+ was 73 times higher than Cr3+ for aza-crown ether containing AC-SBA-15 as an absorbent. The absorbed amount of Co2+ (4.5 x 10(-5) mol/g), Cr3+ (1.5 x 10(-5) mol/g) and Hg2+ (2.25 x 10(-4) mol/g) were remarkably lower than the case of Li+. On the other hand, the absorbed amount of various metal ions of HMC-SBA-15 with amine groups in alky chains and crown ether moieties were 1.1 x 10(-3) mol/g for Li+, 5.0 x 10(-5) mol/g for Co2+, 2.9 x 10(-4) mol/g for Cr3+, 2.8 x 10(-4) mol/g for Hg2+ mol/g, respectively.

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.

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

Antitumor potential of crown ethers: structure-activity relationships, cell cycle disturbances, and cell death studies of a series of ionophores.

Science.gov (United States)

Marjanović, Marko; Kralj, Marijeta; Supek, Fran; Frkanec, Leo; Piantanida, Ivo; Smuc, Tomislav; Tusek-Bozić, Ljerka

2007-03-08

The present paper demonstrates the antiproliferative ability and structure-activity relationships (SAR) of 14 crown and aza-crown ether analogues on five tumor-cell types. The most active compounds were di-tert-butyldicyclohexano-18-crown-6 (3), which exhibited cytotoxicity in the submicromolar range, and di-tert-butyldibenzo-18-crown-6 (5) (IC50 values of approximately 2 microM). Also, 3 and 5 induced marked influence on the cell cycle phase distribution--strong G1 arrest, followed by the induction of apoptosis. A computational SAR modeling effort offers insight into possible mechanisms of crown ether biological activity, presumably involving penetration into cell membranes, and points out structural features of molecules important for this activity. The results reveal that crown ethers possess marked tumor-cell growth inhibitory activity, the extent of which depends on the characteristics of the hydrophilic macrocylic cavity and the surrounding hydrophobic ring. Our work supports the hypothesis that crown ether compounds inhibit tumor-cell growth by disrupting potassium ion homeostasis, which in turn leads to cell cycle perturbations and apoptosis.

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

Partial molar volumes of organic solutes in water. XXVI. 15-Crown-5 and 18-crown-6 ethers at temperatures (298 to 573) K and pressures up to 30 MPa

International Nuclear Information System (INIS)

Cibulka, Ivan

2015-01-01

Highlights: • Density data were obtained in the range T from (298 to 573) K and p up to 30 MPa. • Standard molar volumes of two crown ethers in water are presented. • Group contribution method was designed to estimate standard molar volumes of cyclic ethers. - Abstract: Densities of dilute aqueous solutions of two cyclic ethers, viz. 15-crown-5 and 18-crown-6, measured over the temperature range from (298 to 573) K and at pressures up to 30 MPa using an automated flow vibrating-tube densimeter are reported. Standard molar volumes were evaluated from the measured data. Present data were combined with those obtained previously for several cyclic ethers and predictions of standard molar volumes based on group contribution approach were tested and analysed

Polyaza crown ether as non-nucleosidic building blocks in DNA-conjugates

DEFF Research Database (Denmark)

Jakobsen, Ulla; Rohr, Katja; Madsen, Rasmus K

2007-01-01

The synthesis of amphiphilic polyaza crown ether monomers X (palmityl-substituted), Y (cholesteryl-substituted) and Z (dipalmityl-subtituted) and their incorporation into oligonucleotides are described. Their effects on thermal duplex stability were investigated by UV melting curve analysis. Ther...

Self-Organization of +-Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes

Directory of Open Access Journals (Sweden)

Makoto Tadokoro

2012-01-01

Full Text Available Anionic tris (biimidazolate nickelate (II ([Ni(Hbim3]−, which is a hydrogen-bonding (H-bonding molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is assembled into channel frameworks, approximately 2 nm wide, that clathrate two cationic K+-crown ether derivatives organised into one-dimensional (1D double-columnar arrays. In this study, we have shown that all five cationic guest-included crystals form nanochannel structures that clathrate the 1-D double-columnar arrays of one of the four types of K+-crown ether derivatives, one of which induces a polymorph. This is accomplished by adaptably fitting two types of anionic [Ni(Hbim3]− host arrays. One is a ΔΛ−ΔΛ−ΔΛ⋯ network with H-bonded linkages alternating between the two different optical isomers of the Δ and Λ types with flexible H-bonded [Ni(Hbim3]−. The other is a ΔΔΔ−ΛΛΛ⋯ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim3]− can assemble large cations such as K+ crown-ether derivatives into double-columnar arrays by highly recognizing flexible H-bonding arrangements with two host networks of ΔΛ−ΔΛ−ΔΛ⋯ and ΔΔΔ−ΛΛΛ⋯.

The solvent extraction of carrier-free 90Y from 90Sr with crown ethers

International Nuclear Information System (INIS)

Chuang, J.T.; Lo, J.G.

1995-01-01

A simple solvent extraction method has been developed for the separation of 90 Y from 90 Sr. Crown ether dissolved in chloroform was used as a selective reagent and organic picrate anion was chosen as a counter ion. The effect of various factors on the extraction equilibrium constant of strontium log K ex = 9.15 was obtained from the study of the distribution coefficient versus to crown ether concentration. The separation method was simple, resulted high purity (>99.9%) and quantitative yield, and took less than half an hour. (author) 27 refs.; 4 figs.; 4 tabs

18F-fluorination by crown ether-metal fluoride

International Nuclear Information System (INIS)

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

1984-01-01

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

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.

Theoretical studies on selectivity of dibenzo-18-crown-6-ether for alkaline earth divalent cations

Energy Technology Data Exchange (ETDEWEB)

Heo, Jiyoung [Sangmyung Univ., Seoul (Korea, Republic of)

2012-04-15

Crown ether is one of well-known host molecules and able to selectively sequester metal cation. We employed M06-2X density functional theory with IEFPCM and SMD continuum solvation models to study selectivity of dibenzo-18-crown-6-ether (DB18C6) for alkaline earth dications, Ba{sup 2+}, Sr{sup 2+}, Ca{sup 2+}, and Mg{sup 2+} in the gas phase and in aqueous solution. Mg{sup 2+} showed predominantly strong binding affinity in the gas phase because of strong polarization of CO bonds by cation. In aqueous solution, binding free energy differences became smaller among these dications. However, Mg{sup 2+} had the best binding, being incompatible with experimental observations in aqueous solution. The enthalpies of the dication exchange reaction between DB18C6 and water cluster molecules were computed as another estimation of selectivity in aqueous solution. These results also demonstrated that Mg{sup 2+} bound to DB18C6 better than Ba{sup 2+}. We speculated that the species determining selectivity in water could be 2:1 complexes of two DB18C6s and one dication.

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.

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.

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

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

Molecular modeling study of lithium isotopic separation by crown-ethers in ethanol

International Nuclear Information System (INIS)

Dehez, F.

2002-01-01

The isotopic separation of lithium ion isotopes is studied at the CEA in Pierrelatte using a liquid chromatography technique. Exchange systems are composed by crown-ethers grafted on silica (12C4, 15C5, B15C5, DB15C5, 18C6, B18C6). Lithium is introduced as a salt melted in ethanol. This work concerns the theoretical study of lithium isotopic exchange reactions with those systems. After a brief presentation of isotope separation techniques and isotopic effects (Chap.I), we describe the methods of theoretical chemistry used in this work (Chap. II). In chapter III, we test AM1 and PM3 semi-empirical methods for the treatment of Li + /crown-ether species. Then, we calculate isotopic separation factors via ab initio and semi-empirical calculations for the exchange reactions in vacuum. The different crown-ethers are considered with and without graftings arms. Studies of exchange reactions in ethanol are presented in chapter IV. First, each species of the reaction are solvated by a few ethanol molecules. Isotopic separation factors calculated show a large effect of the solvent on the exchange reaction. The effect of the grafting arm has been investigated using hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics for species with the 12C4. Trajectories have been generated successively with 7 Li and 6 Li. Atomic velocity autocorrelation functions have allowed the access to vibrational frequencies necessary to calculate isotopic separation factors. The last chapter is devoted to methodological developments made during this Ph.D. We propose an approach to treat long range electrostatic interactions in hybrid QM/MM method, relying on a lattice summation technique. (author) [fr

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

SYNTHESIS OF CHIRAL BINAPHTHYL CROWN ETHERS AND THEIR USE IN ANIONIC POLYMERIZATION OF METHYL METHACRYLATE AS INITIATOR LIGANDS

Institute of Scientific and Technical Information of China (English)

Hong-wei Liu; Chuan-fu Chen; Fu Xi

2004-01-01

Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using chiral binaphthyl crown ethers as ligands, respectively. The results showed that in the former case the PMMA obtained has mainly isotactic structure but without optical activity, while in the later case the PMMA produced predominately has syndiotactic suucture also without optical activity.

Radiochemical determination of 210Pb using crown ether

International Nuclear Information System (INIS)

Vajda, N.; Bodizs, D.; Vodicska, M.

1994-01-01

Gamma spectrometric determination of 210 Pb following chemical separation has been performed very precisely and with high sensitivity, due to the low and constant self-absorption of the chemically pure sample. A simple and quick method for the chemical separation of lead using crown ether has been developed. Its four steps are described in detail. The new method was verified using phosphate ore and gypsum samples that were measured in an interlaboratory comparison and with a standard reference material. This method can also be used for self-absorption correction in direct gamma spectrometry of 210 Pb. (N.T.) 4 refs.; 2 figs.; 2 tabs

Removal of technetium from alkaline nuclear-waste media by a solvent-extraction process using crown ethers

International Nuclear Information System (INIS)

Bonnesen, P.V.; Presley, D.J.; Haverlock, T.J.; Moyer, B.A.

1995-01-01

Crown ethers dissolved in suitably modified aliphatic kerosene diluents can be employed to extract technetium as pertechnetate anion (TcO 4 - ) with good extraction ratios from realistic simulants of radioactive alkaline nitrate waste. The modifiers utilized are non-halogenated and non-volatile, and the technetium can be removed from the solvent by stripping using water. The crown ethers bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 (di-t-BuCH18C6) and dicyclohexano-18-crown-6 (DCH18C6) provide stronger TcO 4 - extraction than dicyclohexano-21-crown-7 and 4-tert-butylcyclohexano 15-crown-5. Whereas DCH18C6 provides somewhat higher TcO 4 - extraction ratios than the more lipophilic di-t-BuCH18C6 derivative, the latter was selected for further study owing to its lower distribution to the aqueous phase. Particularly good extraction and stripping results were obtained with di-t-BuCH 18C6 at 0.02 M in a 2:1 vol/vol blend of tributyl phosphate and Isopar reg-sign M. Using this solvent, 98.9% of the technetium contained (at 6 x 10 -5 M) in a Double-Shell Slurry Feed (DSSF) Hanford tank waste simulant was removed following two cross-current extraction contacts. Two cross-current stripping contacts with deionized water afforded removal of 99.1% of the technetium from the organic solvent

Metal ion separations with proton-ionizable Lariat Ethers and their polymers

International Nuclear Information System (INIS)

Bartsch, R.A.

1993-01-01

The preparation of novel and specific organic complexing agents may lead to the development of new separation systems for aqueous metal ions. Thus the introduction of highly lipophilic oximes led to the current utilization of these compounds as commercial extractants for the hydrometallurgy of nonferrous metals. Crown ethers (macrocyclic polyethers) have been employed in the laboratory-scale solvent extraction of alkali-metal, alkaline-earth, and other metal cations into organic phases. Attachment of side arms to crown ethers gives lariat ethers. The presence of one or more potential coordination sites in the side arm of the lariat ether may produce substantial changes in the selectivity and efficiency of metal ion complexation. It has been demonstrated that concomitant transfer of an aqueous phase anion into the organic medium is not required for metal ion extraction. This factor is of immense importance to potential practical applications of these proton-ionizable crown ethers in which the common, hard, aqueous phase anions would be involved. Another advantage of proton-ionizable lariat ethers is the ease with which extracted metal ions may be stripped from the organic phase by shaking with aqueous mineral acid. Thus both metal ion extraction and stripping are facilitated by pendent proton-ionizable groups. Most of the hazardous metal ion species in the Hanford Site tank wastes are members of the alkali-metal, alkaline-earth, lanthanide, and actinide families. These hard metal ion species prefer association with hard donor atoms, such as oxygens. Therefore, crown and lariat ethers are well-suited for complexation with such metal ion species

Progress in radiation chemistry of crown ether extractants used for the solvent extraction of "9"0Sr

International Nuclear Information System (INIS)

Peng Jing; Yu Chuhong; Cui Zhenpeng; Zhai Maolin

2011-01-01

The separation of the long-lived fission products from dissolved nuclear fuel could improve the safe disposal of high-level nuclear wastes and reduce their threaten to human being and environment. Since the extractant system will be exposed to high radiation environment during the solvent extraction of long-lived fission products. The understanding of radiation chemistry of extractants is very important for practical design of extractant system. The radiation chemistry of crown ether systems proposed for use in the solvent extraction of one of fission products "9"0Sr were reviewed based on the study on the radiation stability and radiolysis mechanism of crown ether system. Finally some challenges were suggested. (authors)

Application of capillary affinity electrophoresis and density functional theory to the investigation of benzo-18-crown-6-ether complex with ammonium cation

Czech Academy of Sciences Publication Activity Database

Ehala, Sille; Toman, Petr; Makrlík, E.; Kašička, Václav

2009-01-01

Roč. 1216, č. 45 (2009), s. 7927-7931 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GA203/08/1428; GA AV ČR 1ET400500402 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40500505 Keywords : affinity capillary electrophoresis * benzo-18-crown-6-ether * density functional theory Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.101, year: 2009

Use of open-cell resilient polyurethane foam loaded with crown ether for the preconcentration of uranium from aqueous solutions

International Nuclear Information System (INIS)

Abou-Mesalam, M.M.; El-Naggar, I.M.; Abdel-Hai, M.S.; El-Shahawi, M.S.

2003-01-01

The preconcentration of uranium from aqueous solutions on open-cell resilient polyurethane foams (PUF) impregnated with crown ether as an organic extractant in different conditions was investigated. The data showed that 50 minutes is a sufficient time to attain equilibrium with a maximum extraction percentage for uranium ion on polyurethane foams loaded with crown ether. Also the extraction percentage of uranium is increased markedly with increasing the pH values up to pH ∼ 6 and displayed the lowest extraction at 8 > pH > 6. The different isotherms of uranium sorption have shown that the sorption followed a Freundlich isotherm. Column studies have been carried out in order to extend these studies to the plant scale. From the data of column sorption and breakthrough curves, the height equivalent of theoretical plates (HETP), and breakthrough capacity which affect the efficiency of the column have been calculated and found to be 1.03 mm/plate, 64 ± 5 and 58.3 mg uranium/gram polyurethane foam impregnated with crown ether, respectively. (author)

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

International Nuclear Information System (INIS)

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

1993-01-01

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

Effects of crown ethers in nanocomposite silica-gel electrolytes on the performance of quasi-solid-state dye-sensitized solar cells

KAUST Repository

Huang, Kuan-Chieh

2010-04-01

The effects of crown ethers (CEs) on the performance of quasi-solid-state dye-sensitized solar cells (DSSCs) have been investigated. Nanocomposite silica was used to form gel matrices in the electrolytes, which contained lithium iodide (LiI) and iodine (I2) in 3-methoxypropionitrile (MPN) solvent. Three types of CEs, 12-crown-4 (12-C-4), 15-crown-5 (15-C-5), and 18-crown-6 (18-C-6) were used as additives to the gel electrolytes. DSSCs containing CEs showed enhancements in solar-to-electricity conversion efficiencies (η), with reference to the one without them. The crown ether, 15-C-5, with a size of cavity matching with the size of Li+ in the electrolyte rendered for its DSSC the best performance with an η of 3.60%, under 100 mW/cm2 illumination, as compared to 2.44% for the cell without any CE. Enhancements in the photovoltaic parameters of the cells with the CEs were explained based on the binding abilities of the CEs with lithium ions (Li+) in the electrolyte. Linear sweep voltammetry (LSV) measurements and electrochemical impedance spectra were used to substantiate the explanations. © 2009 Elsevier B.V. All rights reserved.

Design and synthesis of the next generation of crown ethers for waste separations: An inter-laboratory comprehensive proposal. 1998 annual progress report

International Nuclear Information System (INIS)

Alexandratos, S.D.; Chiarizia, R.; Dietz, M.L.; Hay, B.P.; Moyer, B.A.; Sachleben, R.A.

1998-01-01

'The purpose of this task is to undertake the design, synthesis, and characterization of the next generation of crown ethers for metal-ion separations applicable to USDOE''s environmental needs. Target problems include: Li + ions leaching from burial sites at the Oak Ridge Y-12 Plant; fission products 90 Sr and 137 Cs contaminating high-level tank wastes at Hanford, INEEL, and Savannah River; and radium in wastes at the Niagara Falls Storage Site. Unfortunately, the technologies needed to address these problems either do not exist or exhibit substantial deficiencies. Separation techniques such as solvent extraction and ion exchange promise to play a strong role, especially as enhanced with highly selective crown ethers and calixarenes. This project is midway through year 2 of a 3-year effort. Below is given a summary of progress in the approximate period September, 1997, to May, 1998, for each of the four co-investigators at Pacific Northwest National Laboratory (PNNL), Argonne National Laboratory (ANL), Oak Ridge National Laboratory (ORNL), and the University of Tennessee (UTK). The overall approach entails utilization of theory and molecular modeling (PNNL), organic synthesis of novel crown compounds (ORNL), solvent extraction studies (ORNL and ANL), and studies of polymer-immobilized crown ethers (UTK).'

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)

Fine-tuning of electromembrane extraction selectivity using 18-crown-6 ethers as supported liquid membrane modifiers

Czech Academy of Sciences Publication Activity Database

Šlampová, Andrea; Kubáň, Pavel; Boček, Petr

2014-01-01

Roč. 35, č. 23 (2014), s. 3317-3320 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA13-05762S Institutional support: RVO:68081715 Keywords : 18-Crown-6 ethers * electromembrane extraction * inorganic cations * selectivity modification Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.028, year: 2014

Determination of radiostrontium in soil samples using a crown ether

Energy Technology Data Exchange (ETDEWEB)

Vajda, N; Ghods-Esphahani, A; Danesi, P R [International Atomic Energy Agency, Agency' s Laboratories, Chemistry Unit, PCI Laboratory, Seibersdorf (Austria)

1995-07-01

A simple and rapid method has been developed for the separation and successive determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, II. USA), oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours. (author)

Determination of radiostrontium in soil samples using a crown ether

International Nuclear Information System (INIS)

Vajda, N.; Ghods-Esphahani, A.; Danesi, P.R.

1995-01-01

A simple and rapid method has been developed for the separation and successive determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, II. USA), oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours. (author)

THE DISTRIBUTION OF COMMERCIAL CROWN ETHER DC18C6 AND THE EXTRACTION STUDY OF ALKALI AND EARTH ALKALI METALS

Directory of Open Access Journals (Sweden)

Bambang Rusdiarso

2010-06-01

Full Text Available Distribution of A and B isomers of crown-ether DC18C6 on their organic and water phases (chloride, nitrate and sulphocyanide salts and extraction of alkali and earth alkali metals has been studied. In LiCl 0.1 M environment, lithium extraction could be ignored. The presence of extracted potassium metal may affect the crown ether DC18C6 distribution albeit only a little. In KNO3 0.1 M environment, the distribution coefficient values (d were 6.1 and 10.3 for A and B isomers, respectively ; while in KCl  0.1 M environment the values were 4.9 and 11.8, respectively. In KSCN 0.1 M, d values for A and B isomers were 40.4 and 36.6, respectively, which were higher than the value obtained from both KNO3 and KCl  0.1 M environments. Caesium metal extraction using DC18C6 occurred weakly, up to only 5%. Strontium extraction using DC18C6 achieved better yield than the caesium extraction. The percentage of extraction increased under organic solvent according to the following: toluene (4% < chloroform (28% < TBP (35%.   Keywords: distribution, crown-ether DC18C6, extraction.

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

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)

Crown-ether functionalized carbon nanotubes for purification of lithium compounds: computational and experimental study

International Nuclear Information System (INIS)

Singha Deb, A.K.; Arora, S.K.; Joshi, J.M.; Ali, Sk. M.; Shenoy, K.T.; Goyal, Aiana

2015-01-01

Lithium compounds finds several applications in nuclear science and technology, viz, lithium fluoride/hydroxide/alloys are used as dosimetric materials in luminescence devices, molten-salt breeder reactor, international thermonuclear experimental reactor, single crystal based neutron detectors etc. The lithium compounds should be in a proper state of purity; especially it should not contain other alkali metal cations which can downgrade the performance. Hence, there is a need to develop a process for purification of the lithium salt to achieve the desired quality. Therefore an attempt has been made to develop advanced nanomaterials for purification of the lithium salts. In this work, benzo-15-crown-5(B15C5) functionalized carbon nanotubes (CNTs), owing to the good adsorption properties of CNT and alkali metal encapsulation behaviour of B15C5, were showed to bind preferentially with sodium and potassium ions compared to lithium ions. DFT based computation calculations have shown that the free energy of complexation of Na + and K + by B15C5-CNT is higher than that of Li + , implying that B15C5-CNT selectively binds Na + and K + . The experimental batch solid-liquid extraction has also revealed the same trend as in the calculations. The crown-ethers functionalized CNTs have the potentiality for use in purifying lithium compounds. (author)

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...

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.

Novel Naphthalene Based Lariat-Type Crown Ethers Using Direct Single Electron Transfer Photochemical Strategy

International Nuclear Information System (INIS)

Park, Hea Jung; Sung, Nam Kyung; Kim, Su Rhan; Kim, Su Rhan; Ahn, So Hyun; Yoon, Ung Chan; Cho, Dae Won; Mariano, Patrick S.

2013-01-01

This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation Hg 2+ and Pb 2+ showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals

The Synthesis of Novel 3-Substituted Poly(pyrroles) Bearing Crown-ether Moieties and a Study of their Electrochemical Properties

DEFF Research Database (Denmark)

Guernion, Nicolas J.L.; Blencowe, A.; Hayes, Wayne

2006-01-01

A series of fourteen novel pyrrole monomers substituted at the 3-position with aliphatic and aromatic crown-ether moieties have been synthesised in good yield and characterised extensively. Several of those compounds were electropolymerised successfully in acetonitrile, using both potentiostatic ...

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

KAUST Repository

Della Sala, Giorgio

2017-05-31

The fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran with diverse α,β-unsaturated ketones is described. The TBAF catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.

MRI sensing of neurotransmitters with a crown ether appended Gd(3+) complex.

Science.gov (United States)

Oukhatar, Fatima; Même, Sandra; Même, William; Szeremeta, Frédéric; Logothetis, Nikos K; Angelovski, Goran; Tóth, Éva

2015-02-18

Molecular magnetic resonance imaging (MRI) approaches that detect biomarkers associated with neural activity would allow more direct observation of brain function than current functional MRI based on blood-oxygen-level-dependent contrast. Our objective was to create a synthetic molecular platform with appropriate recognition moieties for zwitterionic neurotransmitters that generate an MR signal change upon neurotransmitter binding. The gadolinium complex (GdL) we report offers ditopic binding for zwitterionic amino acid neurotransmitters, via interactions (i) between the positively charged and coordinatively unsaturated metal center and the carboxylate function and (ii) between a triazacrown ether and the amine group of the neurotransmitters. GdL discriminates zwitterionic neurotransmitters from monoamines. Neurotransmitter binding leads to a remarkable relaxivity change, related to a decrease in hydration number. GdL was successfully used to monitor neural activity in ex vivo mouse brain slices by MRI.

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

International Nuclear Information System (INIS)

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

1993-01-01

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

Novel Naphthalene Based Lariat-Type Crown Ethers Using Direct Single Electron Transfer Photochemical Strategy

Energy Technology Data Exchange (ETDEWEB)

Park, Hea Jung; Sung, Nam Kyung; Kim, Su Rhan; Kim, Su Rhan; Ahn, So Hyun; Yoon, Ung Chan [Pusan National Univ., Busan (Korea, Republic of); Cho, Dae Won [Yeungnam Univ., Geoungsan (Korea, Republic of); Mariano, Patrick S. [Univ. of New Mexico, Albuquerque (United States)

2013-12-15

This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation Hg{sup 2+} and Pb{sup 2+} showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

The structure and binding energy of K+endash ether complexes: A comparison of MP2, RI-MP2, and density functional methods

International Nuclear Information System (INIS)

Feller, D.; Apra, E.; Nichols, J.A.; Bernholdt, D.E.

1996-01-01

The structures and binding energies of several cation:ether complexes (K + :dimethyl ether, K + :dimethoxyethane, K + :12-crown-4 and K + :18-crown-6) were determined with second and fourth order perturbation theory using correlation consistent basis sets. Several of these are the largest correlated calculations yet attempted on crown ethers. The observed systematic convergence to the complete basis set limit provides a standard by which the accuracy of previous studies can be measured and facilitates the calibration of density functional methods. Recent Fouier transform ion cyclotron resonance experiments predicted K + :18-crown-6 binding energies which were significantly smaller than ab initio calculations. None of the potential sources of error examined in the present study were large enough to explain this difference. Although the 6-31+G* basis set used in an earlier theoretical study was smaller than the smallest of the correlation consistent basis sets, with suitable correction for basis set superposition error, it appears capable of yielding binding energies within several kcal/mol of the basis set limit. Perturbation theory calculations exploiting the open-quote open-quote resolution of the identity close-quote close-quote approximation were found to faithfully reproduce binding energies and conformational differences. Although the cation endash ether interaction is dominated by classical electrostatics, the accuracy of density functional techniques was found to be quite sensitive to the choice of functionals. The local density SVWN procedure performed well for binding energies and conformational differences, while underestimating K + O distances by up to 0.08 A. The gradient-corrected Becke endash Lee endash Yang endash Parr functional underestimated the K + :12c4 binding energy by 4 endash 7 kcal/mol or 15%. copyright 1996 American Institute of Physics

Crown ethers and phase transfer catalysis in polymer science

CERN Document Server

Carraher, Charles

1984-01-01

Phase transfer catalysis or interfacial catalysis is a syn­ thetic technique involving transport of an organic or inorganic salt from a solid or aqueous phase into an organic liquid where reaction with an organic-soluble substrate takes place. Over the past 15 years there has been an enormous amount of effort invested in the development of this technique in organic synthe­ sis. Several books and numerous review articles have appeared summarizing applications in which low molecular weight catalysts are employed. These generally include either crown ethers or onium salts of various kinds. While the term phase transfer catalysis is relatively new, the concept of using a phasetrans­ fer agent (PTA) is much older~ Both Schnell and Morgan employed such catalysts in synthesis of polymeric species in the early 1950's. Present developments are really extensions of these early applications. It has only been within the last several years that the use of phase transfer processes have been employed in polymer synthesis...

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

Science.gov (United States)

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

2017-06-01

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

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)

Partial Molar Volumes of 15-Crown-5 Ether in Mixtures of N,N-Dimethylformamide with Water.

Science.gov (United States)

Tyczyńska, Magdalena; Jóźwiak, Małgorzata

2014-01-01

The density of 15-crown-5 ether (15C5) solutions in the mixtures of N,N -dimethylformamide (DMF) and water (H 2 O) was measured within the temperature range 293.15-308.15 K using an Anton Paar oscillatory U-tube densimeter. The results were used to calculate the apparent molar volumes ( V Φ ) of 15C5 in the mixtures of DMF + H 2 O over the whole concentration range. Using the apparent molar volumes and Redlich and Mayer equation, the standard partial molar volumes of 15-crown-5 were calculated at infinite dilution ([Formula: see text]). The limiting apparent molar expansibilities ( α ) were also calculated. The data are discussed from the point of view of the effect of concentration changes on interactions in solution.

Magnetic modulation of exciplex fluorescence of pyrene solutions with azacrown-ether excess in the presence of ions of alkali and alkaline earth metals

International Nuclear Information System (INIS)

Borisenko, V.N.; Petrov, N.Kh.; Gromov, S.P.; Alfimov, M.V.

1997-01-01

Photoexcitation of polar pyrene solutions with excess of phenylaza-15-crown-5 as a donor results to intermolecular electron transfer with formation of ion-radical pairs, recombination of which produces fluorescent exciplex. Charge exchange between molecules of crown ether and its cation-radicals is practically absent at that. Magnetic effect, observed for fluorescence, decreases, when adding diamagnetic lithium and calcium ions to exiplex pyrene/crown-ether system. This can be explained by formation of paramagnetic complexes. 15 refs., 5 figs

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

Ab initio and density functional theoretical design and screening of model crown ether based ligand (host) for extraction of lithium metal ion (guest): effect of donor and electronic induction.

Science.gov (United States)

Boda, Anil; Ali, Sk Musharaf; Rao, Hanmanth; Ghosh, Sandip K

2012-08-01

The structures, energetic and thermodynamic parameters of model crown ethers with different donor, cavity and electron donating/ withdrawing functional group have been determined with ab initio MP2 and density functional theory in gas and solvent phase. The calculated values of binding energy/ enthalpy for lithium ion complexation are marginally higher for hard donor based aza and oxa crown compared to soft donor based thia and phospha crown. The calculated values of binding enthalpy for lithium metal ion with 12C4 at MP2 level of theory is in good agreement with the available experimental result. The binding energy is altered due to the inductive effect imparted by the electron donating/ withdrawing group in crown ether, which is well correlated with the values of electron transfer. The role of entropy for extraction of hydrated lithium metal ion by different donor and functional group based ligand has been demonstrated. The HOMO-LUMO gap is decreased and dipole moment of the ligand is increased from gas phase to organic phase because of the dielectric constant of the solvent. The gas phase binding energy is reduced in solvent phase as the solvent molecules weaken the metal-ligand binding. The theoretical values of extraction energy for LiCl salt from aqueous solution in different organic solvent is validated by the experimental trend. The study presented here should contribute to the design of model host ligand and screening of solvent for metal ion recognition and thus can contribute in planning the experiments.

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)

Application of crown ethers to selective extraction and quantitative analysis of technetium 99, iodine 129 and cesium 135 in effluents

International Nuclear Information System (INIS)

Paviet, P.

1992-01-01

Properties of crown ethers are first recalled. Then extraction of technetium 99 is studied in actual radioactive effluents. Quantitative analysis is carried out by liquid scintillation and interference of tritium is corrected. Iodine 129 is extracted from radioactive effluents and determined by gamma spectrometry. Finally cesium 135 is extracted and determined by thermo ionization mass spectroscopy

A colorimetric chiral sensor based on chiral crown ether for the recognition of the two enantiomers of primary amino alcohols and amines.

Science.gov (United States)

Cho, Eun Na Rae; Li, Yinan; Kim, Hee Jin; Hyun, Myung Ho

2011-04-01

A new colorimetric chiral sensor material consisting of three different functional sites such as chromophore (2,4-dinitrophenylazophenol dye), binding site (crown ether), and chiral barrier (3,3'-diphenyl-1,1'-binaphthyl group) was prepared and applied to the recognition of the two enantiomers of primary amino alcohols and amines. Among five primary amino alcohols and two primary amines tested, the two enantiomers of phenylalaninol show the highest difference in the absorption maximum wavelength (Δλ(max)=43.5 nm) and in the association constants (K(S)/K(R)=2.51) upon complexation with the colorimetric chiral sensor material and, consequently, the two enantiomers of phenylalaninol were clearly distinguished from each other by the color difference. Copyright © 2010 Wiley-Liss, Inc.

Optical Sensing of Aromatic Amino Acids and Dipeptides by a Crown-Ether-Functionalized Perylene Bisimide Fluorophore.

Science.gov (United States)

Weißenstein, Annike; Saha-Möller, Chantu R; Würthner, Frank

2018-06-04

The host-guest binding properties of a fluorescent perylene bisimide (PBI) receptor equipped with crown ether were studied in detail with a series of aromatic amino acids and dipeptides by UV/Vis, fluorescence and NMR spectroscopy. Fluorescence titration experiments showed that electron-rich aromatic amino acids and dipeptides strongly quench the fluorescence of the electron-poor PBI host molecule. Benesi-Hildebrand plots of fluorescence titration data confirmed the formation of host-guest complexes with 1:2 stoichiometry. Binding constants determined by global analysis of UV/Vis and fluorescence titration experiments revealed values between 10 3  m -1 and 10 5  m -1 in acetonitrile/methanol (9:1) at 23 °C. These data showed that amino acid l-Trp having an indole group and dipeptides containing this amino acid bind to the PBI receptor more strongly than other amino acids and dipeptides investigated here. For dipeptides containing l-Trp or l-Tyr, the binding strength is dependent on the distance between the ammonium group and the aromatic unit of the amino acids and dipeptides leading to a strong sensitivity for Ala-Trp dipeptide. 1D and 2D NMR experiments also corroborated 1:2 host-guest complexation and indicated formation of two diastereomeric species of host-guest complexes. The studies have shown that a properly functionalized PBI fluorophore functions as a molecular probe for the optical sensing of aromatic amino acids and dipeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Enantiomeric Separation of 1-(Benzofuran-2-yl)alkylamines on Chiral Stationary Phases Based on Chiral Crown Ethers

International Nuclear Information System (INIS)

Park, Soohyun; Kim, Sang Jun; Hyun, Myung Ho

2012-01-01

Optically active chiral amines are important as building blocks for pharmaceuticals and as scaffolds for chiral ligands and, consequently, many efforts have been devoted to the development of efficient methods for their preparation. For example, reduction of amine precursors with chiral catalysts, enzymatic kinetic resolution or dynamic kinetic resolution of racemic amines and the direct amination of ketones with transaminases have been developed as the efficient methods for the preparation of optically active chiral amines. During the process of developing or utilizing optically active chiral amines, the methods for the determination of their enantiomeric composition are essential. Among various methods, liquid chromatographic resolution of enantiomers on chiral stationary phases (CSPs) have been known to be one of the most accurate and economic means for the determination of the enantiomeric composition of optically active chiral compounds. Especially, CSPs based on chiral crown ethers have been successfully used for the resolution of racemic primary amines. For example, CSPs based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (CSP 1, Figure 1) or (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 (CSP 2 and CSP 3, Figure 1) have been known to be quite effective for the resolution of cyclic and non-cyclic amines, various fluoroquinolone antibacterials containing a primary amino group, tocainide (antiarrhythmic agent) and its analogues, aryl-a-amino ketones and 3-amino-1,4-benzodiazepin-2-ones

Decontamination of Metal Ions in Soil by Supercritical CO2 Extraction with Crown Ether

Energy Technology Data Exchange (ETDEWEB)

Park, Jihe; Park, Kwangheon [Kyunghee University, Yongin (Korea, Republic of)

2015-05-15

Previous decontamination methods have shortcomings in that they produce additional waste due to the usage of solutions with chemical toxicity. Hence, demand is strong for new decontamination methods that can guarantee effective decontamination while decreasing the chemical solution. In particular, methods using supercritical CO2 as a means of decontamination are currently in progress. This study examines the method of decontaminating metallic ions inside soil using supercritical CO2. This paper examined the effects of extracting metallic ions inside soil using supercritical CO2 and crown ether as the ligand. It was confirmed that extraction effectiveness increases following greater usage of ligand and co-ligand, with a drastic increase in extraction effectiveness when using extracts over a certain dose. Moreover, it was shown that if the usage of ligand and additive decreases, the extraction ratio also decreases.

Decontamination of Metal Ions in Soil by Supercritical CO2 Extraction with Crown Ether

International Nuclear Information System (INIS)

Park, Jihe; Park, Kwangheon

2015-01-01

Previous decontamination methods have shortcomings in that they produce additional waste due to the usage of solutions with chemical toxicity. Hence, demand is strong for new decontamination methods that can guarantee effective decontamination while decreasing the chemical solution. In particular, methods using supercritical CO2 as a means of decontamination are currently in progress. This study examines the method of decontaminating metallic ions inside soil using supercritical CO2. This paper examined the effects of extracting metallic ions inside soil using supercritical CO2 and crown ether as the ligand. It was confirmed that extraction effectiveness increases following greater usage of ligand and co-ligand, with a drastic increase in extraction effectiveness when using extracts over a certain dose. Moreover, it was shown that if the usage of ligand and additive decreases, the extraction ratio also decreases

Selective cesium removal from radioactive liquid waste by crown ether immobilized new class conjugate adsorbent.

Science.gov (United States)

Awual, Md Rabiul; Yaita, Tsuyoshi; Taguchi, Tomitsugu; Shiwaku, Hideaki; Suzuki, Shinichi; Okamoto, Yoshihiro

2014-08-15

Conjugate materials can provide chemical functionality, enabling an assembly of the ligand complexation ability to metal ions that are important for applications, such as separation and removal devices. In this study, we developed ligand immobilized conjugate adsorbent for selective cesium (Cs) removal from wastewater. The adsorbent was synthesized by direct immobilization of dibenzo-24-crown-8 ether onto inorganic mesoporous silica. The effective parameters such as solution pH, contact time, initial Cs concentration and ionic strength of Na and K ion concentrations were evaluated and optimized systematically. This adsorbent was exhibited the high surface area-to-volume ratios and uniformly shaped pores in case cavities, and its active sites kept open functionality to taking up Cs. The obtained results revealed that adsorbent had higher selectivity toward Cs even in the presence of a high concentration of Na and K and this is probably due to the Cs-π interaction of the benzene ring. The proposed adsorbent was successfully applied for radioactive Cs removal to be used as the potential candidate in Fukushima nuclear wastewater treatment. The adsorbed Cs was eluted with suitable eluent and simultaneously regenerated into the initial form for the next removal operation after rinsing with water. The adsorbent retained functionality despite several cycles during sorption-elution-regeneration operations. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Complete separation of racemic p-boronophenylalanine by high performance liquid chromatography with crown ether-coated reversed-phase packings

International Nuclear Information System (INIS)

Yoshino, K.; Mieda, S.; Maruyama, T.; Mori, Y.; Mishima, Y.; Ichihashi, M.

1992-01-01

Since the L-form of p-boronophenylalanine (p-bpa) has been shown to be more efficiently incorporated into melanoma cells than racemic p-bpa separation of racemic p-bpa into its stereoisomers is an important subject. One of the preparative methods used to resolve racemic p-bpa involves the use of α-chymotrypsin. However, there has been a problem in that optical purity of resolved L- or D-p-bpa products was not easily determined. In this paper, the authors describe a method which can be used to confirm the optical purity of b-pba using high performance liquid chromatography (HPLC) with crown ether-coated reversed-phase packings

A novel technique for the simultaneous determination of 210Pb and 210Po using a crown ether

International Nuclear Information System (INIS)

Vajda, N.; LaRosa, J.; Zeisler, R.; Danesi, P.; Kis-Benedek, Gy.

1997-01-01

A simple radiochemical procedure has been developed to separate lead and polonium simultaneously from different environmental and biological materials. After adding 208 Po tracer and lead carrier, samples are decomposed using mineral acids. Lead and polonium are selectively retained from 2M HCl solution by the bis-4,4'(5')-t-butyl-cyclohexano-18-crown-6-ether; polonium is stripped with 6 M HNO 3 while lead is stripped with 6 M HCL solution. A polonium source is prepared by spontaneous deposition onto a silver disk. The activity concentration of 210 Po is determined by isotope dilution alpha spectrometry. Lead is precipitated as oxalate; the chemical recovery is determined by gravimetry. The activity concentration of 210 Pb is calculated from the liquid scintillation spectrum. (author)

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

International Nuclear Information System (INIS)

Knoechel, A.; Wilken, R.D.

1981-01-01

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

Fast Potentiometric Analysis of Lead in Aqueous Medium under Competitive Conditions Using an Acridono-Crown Ether Neutral Ionophore

Directory of Open Access Journals (Sweden)

Ádám Golcs

2018-05-01

Full Text Available Lead is a particularly toxic heavy metal that is present above acceptable levels in the water of many countries. This article describes a quick detection method of lead(II ions using a polyvinyl chloride (PVC-based ion-selective membrane electrode containing an acridono-crown ether ionophore by potentiometry. The electrochemical cell exhibits a Nernstian response for lead(II ions between the concentration range of 10−4 to 10−2 M, and can be used in the pH range of 4–7. The applicability of this sensor was verified by measuring a multicomponent aqueous sample. Under the given conditions, this electrode is suitable for the selective quantitative analysis of lead(II ions in the presence of many additional metal ions.

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)

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.

High Resolution Rotational Spectroscopy of a Flexible Cyclic Ether

Science.gov (United States)

Gámez, F.; Martínez-Haya, B.; Blanco, S.; López, J. C.; Alonso, J. L.

2011-06-01

Crown ethers stand as one cornerstone molecular class inhost-guest Supramolecular Chemistry and constitute building blocks for a broad range of modern materials. We report here the first high resolution rotational study of a crown ether: 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5 ether,15c5). Molecular beam Fourier transform microwave spectroscopy has been employed. The liquid sample of 15c5 has been vaporized using heating methods. The considerable size of 15c5 and the broad range of conformations allowed by the flexibility of its backbone pose important challenges to spectroscopy approaches. In fact, the ab-initio computational study for isolated 15c5, yields at least six stable conformers with relative free energies within 2 kJ Mol-1 (167 Cm-1). Nevertheless, in this investigation it has been possible to identify and characterize in detail one stable rotamer of the 15c5 molecule and to challenge different quantum methods for the accurate description of this system. The results pave the ground for an extensive description of the conformational landscape of 15c5 and related cyclic ethers in the near term. J. L. Alonso, F. J. Lorenzo, J. C. López, A. Lesarri, S. Mata and H. Dreizler, Chem. Phys., 218, 267 (1997) S. Blanco, J.C López, J.L. Alonso, P. Ottaviani, W. Caminati, J. Chem. Phys. 119, 880 (2003) S.E. Hill, D. Feller, Int. J. Mass Spectrom. 201, 41 (2000)

Alkaline-side extraction of technetium from tank waste using crown ethers and other extractants

International Nuclear Information System (INIS)

Bonnesen, P.V.; Moyer, B.A.; Presley, D.J.; Armstrong, V.S.; Haverlock, T.J.; Counce, R.M.; Sachleben, R.A.

1996-06-01

The chemical development of a new crown-ether-based solvent-extraction process for the separation of (Tc) from alkaline tank-waste supernate is ready for counter-current testing. The process addresses a priority need in the proposed cleanup of Hanford and other tank wastes. This need has arisen from concerns due to the volatility of Tc during vitrification, as well as 99 Tc's long half-life and environmental mobility. The new process offers several key advantages that direct treatability--no adjustment of the waste composition is needed; economical stripping with water; high efficiency--few stages needed; non-RCRA chemicals--no generation of hazardous or mixed wastes; co-extraction of 90 Sr; and optional concentration on a resin. A key concept advanced in this work entails the use of tandem techniques: solvent extraction offers high selectivity, while a subsequent column sorption process on the aqueous stripping solution serves to greatly concentrate the Tc. Optionally, the stripping solution can be evaporated to a small volume. Batch tests of the solvent-extraction and stripping components of the process have been conducted on actual melton Valley Storage Tank (MVST) waste as well as simulants of MVST and Hanford waste. The tandem process was demonstrated on MVST waste simulants using the three solvents that were selected the final candidates for the process. The solvents are 0.04 M bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 (abbreviated di-t-BuCH18C6) in a 1:1 vol/vol blend of tributyl phosphate and Isopar reg-sign M (an isoparaffinic kerosene); 0.02 M di-t-BuCH18C6 in 2:1 vol/vol TBP/Isopar M and pure TBP. The process is now ready for counter-current testing on actual Hanford tank supernates

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

to the cation charge accounts for 20 to 26% of the total electrostatic energy, which is much higher than for complexes with crown-ethers. Atomic charge fluctuations were calculated on BC6 during simulations in aqueous solution and were compared with gas phase values. Figure 4 shows that the charges on non-coordinated oxygen atoms slightly increase in the aqueous phase, but change very strongly for the atoms coordinated to the cation, particularly in the sodium complex, Similarly, the carbon atoms of the chelating aromatic cavity are overall more polarized with the cesium complex (total charge -1.06 e) than with the sodium complex (total charge -0.965 e). This analysis illustrates, in qualitative terms, the role of cation - n interactions present in the cesium complex. It also stresses the crudeness of the approximations made in most standard dynamics simulations, in which the total electrostatic contribution is evaluated using fixed charges derived from the free ligand. Whatever the method used, the structure of the cesium complex is correctly reproduced. This is partly due to a suitable structural complementarity, which drastically reduces the number of degrees of freedom. However, the structure of the sodium complex is very dependent on the presence of the counter-ion, as well as the parameters and the method employed. The experimental data show that sodium is at the top of the crown with a water molecule located under the cation. In fact, in this QM/MM simulation, we find a cation at the top of the crown, but during the simulated time the water molecules remain in a facial position. This hybrid approach avoids the problem of calculating effective point charges, the main source of uncertainties in classical dynamics. It allows an accurate computation of the electrostatic energy, explicitly accounting for the non-additive terms due to polarization of the ligand by the cation and solvent, particularly the cation - π interactions. (authors)

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

International Nuclear Information System (INIS)

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

1988-01-01

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

Thermodynamic and electrochemical properties of some rare earth cryptates and related complexes in propylene carbonate

International Nuclear Information System (INIS)

Loufouilou, E.L.

1986-03-01

The stability of trivalent lanthanide complexes with [1]-cryptand 22 and [2]-cryptands 222 and 211 and also tris (3.6- dioxa heptyl) amine (TDHA) is studied in propylene carbonate solution by potentiometry with Ag + as an auxiliary cation. Complexation enthalpies and entropies are determined for other complexes of some trivalent lanthanides (La, Er, Pr and Eu) with ligands 222, 221, 211, 22, 21, 18C6 and TDHA. [1]- and [2]- crytands are complexing agents more powerful than TDHA and crown-ethers 15C6 and 18C6. For ligands containing nitrogen complexe stability increase with RE atomic number but decrease for crown-ethers. In propylene carbonate complexes are stabilized by enthalpic effects, entropic contribution is variable. Polarographic reduction of samarium cryptate with ligand 222, 221 and 22 in propylene carbonate is reversible as in more solvating solvents water and methanol. Mixed complexes are formed with chlorides and this cryptate system is more difficult to reduce [fr

Combination of size selective binding ability of 18-crown-6 dissolved in aqueous phase and extractive properties of an amic acid; toward enhancement of rare earths separation

Energy Technology Data Exchange (ETDEWEB)

Safarbali, Reyhaneh; Yaftian, Mohammad Reza; Ghorbanloo, Massomeh [Zanjan Univ. (Iran, Islamic Republic of). PhaseEquilibria Research Lab.; Zamani, Abbasali [Zanjan Univ. (Iran, Islamic Republic of). Environmental Science Research Lab.

2016-11-15

The separation of La(III), Eu(III) and Er(III) ions by an amic acid, N,N-dioctyldiglycolamic acid (HL), dissolved in carbon tetrachloride has been improved in the presence of 18-crown-6 (18C6) in aqueous phase as a selective masking agent. The interaction between the studied metal ions and 18C6 resulted a shift in the extraction curve of the studied metal ions versus pH toward higher pH region. The displacement of the extraction curves was more pronounced for lanthanum ions and was varied as La(III) > Eu(III) > Er(III). This order of complexing ability of 18C6 toward the studied ions was attributed to the size adaptation of the ions and that of the crown ether cavity. The stability constants of the lanthanide-crown ether complexes in aqueous phase were evaluated. The influence of temperature on the extraction of studied metal ions from aqueous phase in the absence and the presence of 18C6 was tested in the range 298-308 K. This investigation allowed evaluating the thermodynamic parameters associated with the extraction process and those of the complexation of cations by 18C6 in the aqueous phase.

Binary vapour—liquid equilibria of methanol with sulfolane. Tetraethylene glycol dimethyl ether and 18-crown-6 = Phasengleichgewichte in binären systemen von Methanol mit Sulfolan, Tetraethylenglycoldimethylether und 18-krone-6 Kronenether

NARCIS (Netherlands)

Kuczynski, M.; 't Hart, W.; Westerterp, K.R.

1986-01-01

The activity coefficients of methanol in sulfolane, tetraethylene glycol dimethyl ether (TEGDME) and 18-crown-6 under conditions of equilibrium have been determined in the temperature range 423–503 K and in the pressure range 0.28–3.5 MPa. A minimum in the activity coefficient was found for the

Synthesis of Novel Bibrachial Lariat Ethers (BiBLEs) Containing [1,2 ...

African Journals Online (AJOL)

NICO

A practical and regioselective method for the synthesis of cis-diastereomers of bibrachial lariat ethers (BiBLEs) bearing ester and amide groups is reported. The novel bibrachial lariat ethers (BiBLEs) 3a–d with neutral side chains were prepared by reaction of the corresponding aza-crown macrocycles 1a–b with ethyl ...

Flourimetric and prototropic studies on the inclusion complexation of 2-amino and 4-aminodiphenyl ethers with {beta}-cyclodextrin: Unusual behavior of 4-aminodiphenyl ether

Energy Technology Data Exchange (ETDEWEB)

Enoch, Israel V. Muthu Vijayan [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India); Swaminathan, Meenakshisundaram [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India)], E-mail: chemsam@yahoo.com

2007-12-15

The fluorescence characteristics of diphenyl ether (DPE), 2-aminodiphenyl ether (2ADPE) and 4-aminodiphenyl ether (4ADPE) and prototropic behavior of 2ADPE and 4ADPE on inclusion complexation with {beta}-cyclodextrin have been investigated. DPE forms 1:1 complex whereas 2ADPE and 4ADPE form 1:2 complex with {beta}-CDx. The fluorimetric and prototropic behaviors of 4ADPE in {beta}-CDx are different from those in aqueous solution. The dual fluorescence of 4ADPE in {beta}-CDx is found to be due to twisted intramolecular charge transfer (TICT) character induced by inclusion complexation. The two equilibria viz. monocation{r_reversible}monocation solvent exciplex{r_reversible}neutral reported for 4ADPE in aqueous solution are not observed in presence of {beta}-CDx. The ground and excited state pK{sub a} values for monocation-neutral equilibrium of 2ADPE and 4ADPE have been reported.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-03-01

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

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.)

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.

Extraction of metals such as Pu, U and Sr with an organic solvent or a solid phase containing a cis-syn-cis isomer of the crown ether DCH18C6

International Nuclear Information System (INIS)

Guy, A.; Foos, J.; Lemaire, M.; Guyon, V.; Chomel, R.; Doutreluigne, P.; Le Roy, H.

1991-01-01

The cis-syn-cis isomer of the crown ether DCH18C6 is used in solution in an organic diluent such as benzonitrile or dichlorethane, or on a solid phase such as silica. The use of this isomer increases the extraction ratio of plutonium and strontium of solution from spent fuel reprocessing or from aqueous effluents containing Sr or Pu [fr

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.

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 -

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.

Chemoselective Activation of Trimethylsilyl Enol Ether Functionalities in the Presence of Silyl-Protected Alcohols by Trimethylsilyl-Nonaflyl Exchange

Czech Academy of Sciences Publication Activity Database

Boltukhina, Ekaterina; Sheshenev, Andrey; Lyapkalo, Ilya

-, č. 21 (2011), s. 3507-3515 ISSN 0039-7881 Institutional research plan: CEZ:AV0Z40550506 Keywords : biphasic catalysis * crown ether * sulfonylating reagent * trialkylsilyl ethers * alkenyl nonaflates Subject RIV: CC - Organic Chemistry Impact factor: 2.466, year: 2011

A distribution ratio model of strontium by crown ether extraction from simulated HLLW

International Nuclear Information System (INIS)

Chen Jing; Wang Qiuping; Wang Jianchen; Song Chongli

1995-01-01

An experiential distribution ratio model for strontium extraction by dicyclohexano-18-crown-6-n-octanol from simulated high-level waste is established. The experimental points for the model are designed by experimental homogeneous-design method. The regression of distribution ratio model of strontium is carried out by the complex-optimization method. The model is verified with experimental distribution ratio data in different extraction conditions. The results show that the relative deviations are within +-10% and the mean relative divination is 4.4% between the calculated data and the experimental ones. The experiential model together with an iteration program can be used for the strontium extraction process calculation

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)

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

Science.gov (United States)

Coutrot, Frédéric

2015-10-01

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

Effect of γ radiation on the solution of potassium permanganate complex with di-tert.-butyl-dibenzo-18-crown-6 in benzene

International Nuclear Information System (INIS)

Makhlyarchuk, V.V.; Zatonskij, S.V.; Mikhajlenko, I.E.; Saraeva, V.V.

1987-01-01

Effect of 60 Co gamma-radiation on benzene containing KMnO 4 solubilized with crown-ether is studied. Radiation was carried out at room temperature with doses up to 28 kGy at dose rate of 3.9 Gy/s. Sharp increase of diphenyl yield and absence of phenylcyclohexadiene (PCH) in radiolysis products points out interaction of permanganate-ion with predecessors of PCH formation. High yield of permanganate decomposition results from reactions with excited molecules of the solvent

Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

KAUST Repository

Kumar, Rajeev Ananda; De, Priyadarsi; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2015-01-01

The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.

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

International Nuclear Information System (INIS)

Fux, P.

1984-06-01

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

Role of Interfacial Properties of 4-hydroxyquinoline and / or Some Crown Ethers in the Mechanism of Extraction Process

International Nuclear Information System (INIS)

Daoud, J.A.; El-Dessouky, S.I.

2000-01-01

The interfacial properties of 8-hydroxyquinoline (HOX) and /or some crown ethers; Db 18 C6, 18 C6 and 15 C5 at the chloroform/ nitrate interface were investigated by measuring their interfacial tension using Du Nouy ring method. The data indicate that 18 C6 and 15 C5 have variable effects on the chloroform-nitrate interface according to their concentrations while Db 18 C6 and HOX have nearly no effect at the interface in the investigated concentration range. The mixture of HOX and 18 C6 or 15 C5 showed different trends according to their concentrations. The proposed mechanisms were verified by carrying out Co(II) extraction by HOX-Db 18 C6 mixture in chloroform in the low and high concentration ranges at different interfacial area. The use of benzene instead of chloroform indicate that the nature of diluent has a marked effect on the interfacial properties of 18 C6 and 15 C5 while Db 18 C6 was found to be sparingly soluble in benzene in the investigated concentration range

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2014-01-01

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda

2014-03-25

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

/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.

Toluidine blue-sodium lauryl ether sulfate complexes : Influence of ethylene oxide length

NARCIS (Netherlands)

Vleugels, L.F.W.; Féat, A.; Voets, I.K.; Tuinier, R.

2017-01-01

Sodium Lauryl Ether Sulfates (SLES) are an increasingly important and versatile type of surfactants. The complexation between ortho-Toluidine blue (TBO) and a homologous series of SLES, including Sodium Lauryl Sulfate (SDS) without Ethylene Oxide (EO), has been investigated using visible

Crown bridged thiacalix[4]arenes as cesium-selective ionophores in solvent polymeric membrane electrodes

International Nuclear Information System (INIS)

Bereczki, Robert; Csokai, Viktor; Gruen, Alajos; Bitter, Istvan; Toth, Klara

2006-01-01

Novel 1,3-alternate thiacalix[4]mono- and biscrown-6 ethers were studied as ionophores in poly(vinyl chloride) membrane electrodes. Their selectivity behavior was characterized with respect to large number of cations, including potential interferents in environmental samples, and the membrane composition was optimized for cesium ion response. Among the ionophores, 1,3-alternate thiacalix[4]mono(crown-6) ether showed, especially high selectivity for cesium over other alkali-metal ions. Transition and heavy metal ions did not interfere seriously with the electrode response, which indicates that the bridging sulfur atoms do not take part in the ion recognition process. The potentiometric cesium responses of all electrodes involved in this study were found close to Nernstian and the detection limits were lower than 10 -7 M. The Cs + /Na + selectivity of the different ionophore-based sensors and the solvent extraction ability of the ligands were interpreted based on the respective constants of complex formation

Influence of polyether ring size and of the nature of substituents on the yields of paramagnetic centers in γ-irradiated mono- and dibenzosubstituted crown ethers at 77 K

International Nuclear Information System (INIS)

Nesterov, S.V.; Panov, O.Yu.

1998-01-01

Intermediates stabilized in γ-irradiated mono- and dibenzosubstituted crown ethers are studied by ESR spectroscopy at 77 K. PhO · radicals and radicals with H-atom abstraction from polyether ring are the main products at low temperature γ-radiolysis. The nature of radicals produced in radiolysis and the yield of radicals, G R , depend on macroring size and on the number of aromatic substituents. Negative deviation from additive rule in function of G R versus ε of substituents is an evidence of efficient transfer of adsorbed energy to the π-system of aromatic group. (author)

Reaksi Penataan Ulang Sigmatropik Hidrogen [1,3] Secara Termal dan Reaksi Penataan Ulang Prototropik [1,3] yang dikatalisis oleh Katalis Transfer Fase (Ptc , [18]-Crown Ether-6: Semi-Sintesis Vanili dari Eugenol

Directory of Open Access Journals (Sweden)

Hendra Wijaya

2002-04-01

Full Text Available Semi-synthesis of vanillin from eugenol can be divided into two step reactions namely, isomerization of eugenol intoisoeugenol, and cleavage oxidation of isomerization product into expected reaction product (vanillin. In this work isomerization of eugenol or eugenyl acetate into isoeugenol or isoeugenyl acetate has been done via the following reactions: (1 Sigmatropic hydrogen (1,3 thermalic rearrangement reaction: direct heating of eugenol or eugenyl acetate at 220oC for 8 hours can produce 52.2% of isoeugenol or 65.7% of isoeugenyl acetate (both chemical yields are measured by means nmr-spectrometer, where products are viscose yellow-brownish liquid as mixture of unseparated starting material and isomerization product. (2 Prototropic (1,3 rearrangement catalyzed by phase transfer catalyst (PTC: (18-crown ether-6 at room temperature can be afforded 71.4% of isoeugenol as light yellow liquid (mixture of unseparated starting material and isomerization product. Without any separation of mixture between isomerization product and starting material followed by subsequent cleavage oxidation using KMnO4 as oxidator in neutral condition catalyzed by phase transfer catalyst: (18-crown ether-6 at room temperature for 3 hours can be yielded 16.5-22.9% of vanillin (from the starting material; eugenol or eugenyl acetate. The spectroscopical data of synthetical vanillin is not rather different with the spectroscopical data of authentical natural vanillin.

Structure and reactivity of boron-ate complexes derived from primary and secondary boronic esters.

Science.gov (United States)

Feeney, Kathryn; Berionni, Guillaume; Mayr, Herbert; Aggarwal, Varinder K

2015-06-05

Boron-ate complexes derived from primary and secondary boronic esters and aryllithiums have been isolated, and the kinetics of their reactions with carbenium ions studied. The second-order rate constants have been used to derive nucleophilicity parameters for the boron-ate complexes, revealing that nucleophilicity increased with (i) electron-donating aromatics on boron, (ii) neopentyl glycol over pinacol boronic esters, and (iii) 12-crown-4 ether.

An improved synthesis process of calixcrown ethers and synthesis of novel calixcrown ether

International Nuclear Information System (INIS)

Wang Hairong; Zhang Ping; Wang Chunmiao; Wang Jianchen; Chen Jing

2007-01-01

The synthesis method of calixcrown ethers was simplified and improved, and 10 L- scale synthesis was carried out. In the synthesis of the intermediates of the first three steps, the synthesis of 5, 11, 17, 23-tetra-tert-butyl-25, 26, 27, 28-tetrahydroxyl-calix[4] and its dehydroxylation were considered together, the purification procedures of the former, including re-crystallization in toluene and decolorization with activated carbon, were cancelled, and thus these steps were simplified. In the synthesis of oligoethylene glycol ditosylate, the purification method was also improved and the time-consuming column chromatography was left out. In the final step, impurities were removed by repeating stirring-settlement steps, by following recrystallization, the pure product was obtained. With these measures, the whole process could be implemented easily. The industrial scale production of calixcrown ethers could be fulfilled with the improved process. In addition, a new extracant, 25, 27-bis (n-propyloxy)calix[4]-26, 28-crown-6, is prepared and identified. (authors)

Polycation–sodium lauryl ether sulfate-type surfactant complexes : influence of ethylene oxide length

NARCIS (Netherlands)

Vleugels, L.F.W.; Pollet, J.; Tuinier, R.

2015-01-01

Polyelectrolyte-surfactant complexes (PESC) are a class of materials which form spontaneously by self-assembly driven by electrostatic and hydrophobic interactions. PESC containing sodium lauryl ether sulfates (SLES) have found wide application in hair care products like shampoo. Typically, SLES

Polycation-Sodium Lauryl Ether Sulfate-Type Surfactant Complexes : Influence of Ethylene Oxide Length

NARCIS (Netherlands)

Vleugels, Leo F. W.; Pollet, Jennifer; Tuinier, Remco

2015-01-01

Poiyelectrolyte-surfactant complexes (PESC) are a class of materials which form spontaneously by self-assembly driven by electrostatic and hydrophobic interactions. PESC containing sodium lauryl ether Sulfates (SLES) have found wide application in hair care products like shampoo. Typically, SLES

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

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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

Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn).

Science.gov (United States)

Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

2012-10-15

Heavy metals are both a problem for the environment and an important resource for industry. Their selective extraction by means of organic ligands therefore is an attractive topic. The coordination of three thiacrown ethers to late 3d-metal ions was investigated by a combination of electrospray ionization mass spectrometry (ESI-MS) and electron paramagnetic resonance (EPR). The mass spectrometric experiments were carried out in an ion trap mass spectrometer with an ESI source. Absolute binding constants were estimated by comparison with data for 18-crown-6/Na(+). EPR spectroscopy was used as a complementary method for investigating the Cu(I) /Cu(II) redox couple. The study found that thiacrown ethers preferentially bind traces of copper even at an excess of other metal ions (Co(II), Ni(II), and Zn(II)). The absolute association constants of the Cu(I) complexes were about 10(8) M(-1), and about two orders of magnitude lower for the other 3d-metal cations. The EPR spectra demonstrated that the reduction from Cu(II) to Cu(I) upon formation of the [(thiacrown)Cu](+) species takes place in solution. ESI-MS demonstrated that the three thiacrown ligands examined had high binding constants as well as good selectivities for copper(I) at low concentrations, and in the presence of other metal ions. By a combination of ESI-MS and EPR spectrometry it was shown that the reduction from Cu(II) to Cu(I) occurred in solution. Copyright © 2012 John Wiley & Sons, Ltd.

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 -

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)

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

International Nuclear Information System (INIS)

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

1994-01-01

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

Oxidation mechanism of diethyl ether: a complex process for a simple molecule.

Science.gov (United States)

Di Tommaso, Stefania; Rotureau, Patricia; Crescenzi, Orlando; Adamo, Carlo

2011-08-28

A large number of organic compounds, such as ethers, spontaneously form unstable peroxides through a self-propagating process of autoxidation (peroxidation). Although the hazards of organic peroxides are well known, the oxidation mechanisms of peroxidizable compounds like ethers reported in the literature are vague and often based on old experiments, carried out in very different conditions (e.g. atmospheric, combustion). With the aim to (partially) fill the lack of information, in this paper we present an extensive Density Functional Theory (DFT) study of autoxidation reaction of diethyl ether (DEE), a chemical that is largely used as solvent in laboratories, and which is considered to be responsible for various accidents. The aim of the work is to investigate the most probable reaction paths involved in the autoxidation process and to identify all potential hazardous intermediates, such as peroxides. Beyond the determination of a complex oxidation mechanism for such a simple molecule, our results suggest that the two main reaction channels open in solution are the direct decomposition (β-scission) of DEE radical issued of the initiation step and the isomerization of the peroxy radical formed upon oxygen attack (DEEOO˙). A simple kinetic evaluation of these two competing reaction channels hints that radical isomerization may play an unexpectedly important role in the global DEE oxidation process. Finally industrial hazards could be related to the hydroperoxide formation and accumulation during the chain propagation step. The resulting information may contribute to the understanding of the accidental risks associated with the use of diethyl ether.

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

International Nuclear Information System (INIS)

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

1987-01-01

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

Investigation of ammonium trinitratouranylate complexing with diethyl ether

International Nuclear Information System (INIS)

Khod'ko, N.N.; Kolevich, T.A.; Umrejko, D.S.

1989-01-01

Interaction of ammonium trinitratouranylate (ATNU) with diethyl ether is investigated. It is shown, that adduct of UO 2 (NO 3 ) 2 · 2(C 2 H 5 ) 2 O coposition is formed in the indicated solvent due to incongruent solubility of ANTU. Analogous compound is obtained at ether effect on uranyl anhydrous nitrate. The matter is determined and investigated by means of chemical, thermal analyses and oscillating spectroscopy

Spectroscopic (IR, NMR) and conductometric characterization of lithium aluminum hydride - crown ethers complexes [Li{sup +}-C E](A I H{sub 4})- with C E=syn-isomers of DC 18-C-6 in benzene solutions; Caracterisation par spectrometrie (IR, RMN) et conductimetrie des complexes entre le tetrahydrualuminate de lithium LiAIH{sub 4} et l`ether-couronne DC 18-C-6* (isomeres cis-anti-cis et cis-syn-cis) en solution dans le benzene (*2,3,11,12-dicyclohexano-1,4,7,10,13,16-hexacyclooctadecane)

Energy Technology Data Exchange (ETDEWEB)

Bastide, J P; Ezzemouri, K; Carre, J; Bouamrane, A; Claudy, P [Institut National des Sciences Appliquees (INSA), 69 - Villeurbanne (France); Frange, B [Faculte des Sciences, 21 - Dijon (France)

1996-03-01

[Li{sup +}-C E](AIH{sub 4}){sup -} complexes with C E = syn and anti-isomers of the crown ether DC 18-C-6 have been characterized in benzene solutions by IR (infrared spectroscopy), NMR (nuclear magnetic resonance) and conductometry (at 298 K). The properties of these complexes are closely related to those of the cation [Li{sup +}-C E]. For the anti-isomer, no distortion of the macrocycle was noticed after complexation, the Li{sup +} trapped cation is coordinated with four oxygen atoms of the cavity, and the complex exhibits a covalent behavior. Electrical conductivity of the benzene solution is concentration independent and has a very low mean value ({lambda} = 0,06 {omega}{sup -1}.cm{sup 2}.mol{sup -1}). The macrocycle of the syn-isomer is drastically distorted after complexation. A tridimensional cavity is formed, in which the Li{sup +} trapped cation is coordinated with six oxygen atoms. As a consequence, the species exhibits a high degree of ionic character due to the stretching of the Li{sup +}---(AIH{sub 4}){sup -} bond. Electrical conductivity is enhanced for dilute solutions (x 10 at C 0,01 mol.L{sup -1}). The regular tetrahedral symmetry of (AIH{sub 4}){sup -} anion is retained in the molecular structure of the two complexes. Benzene solutions of [Li-+-syn-DC 18-C-6](AIH{sub 4}){sup -} appear to be the first example of free-(AIH{sub 4}){sup -} anions in a non-polar organic medium. (authors). 22 refs., 3 figs., 4 tabs.

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

International Nuclear Information System (INIS)

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

1994-01-01

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

All solid supercapacitor based on polyaniline and crosslinked sulfonated poly[ether ether ketone

International Nuclear Information System (INIS)

Sivaraman, P.; Kushwaha, R.K.; Shashidhara, K.; Hande, V.R.; Thakur, A.P.; Samui, A.B.; Khandpekar, M.M.

2010-01-01

All solid supercapacitor based on polyaniline (PANI) and crosslinked sulfonated poly[ether ether ketone] (XSPEEK,) is reported in this paper. The crosslinker used for sulfonated poly[ether ether ketone] (SPEEK) is 1,4-bis(hydroxymethyl) benzene. The XSPEEK is used as both solid electrolyte and separator membrane. Supercapacitors are fabricated using various PANI/XSPEEK weight ratios. These are characterized by cyclic voltammetry and galvanostatic charge-discharge studies. The supercapacitor with PANI/XSPEEK weight ratio 1:0.5, exhibit a specific capacitance of 480 F g -1 of PANI. To the best of authors' knowledge, the value reported here is the highest for a supercapacitor based on a proton conducting solid polymer electrolyte and PANI. Detailed electrochemical impedance spectroscopy analysis is carried out. The analysis shows that the complex capacitance of the supercapacitor depends on the XSPEEK content. The time constant (t 0 ), derived from the imaginary part of complex capacitance decreases with increase in the XSPEEK content in the supercapacitor. Cycle life characteristics of the supercapacitor show a decrease in specific capacitance during initial cycles and get stabilized during later cycles.

Cation or Solvent-Induced Supermolecular Phthalocyanine Formation: Crown Ether Substituted Phthalocyanines.

Science.gov (United States)

1987-06-01

spectra were obtained with a Varian SF330 spectrofluorimeter with appropriate filters to eliminate scattered light. Fluorescence quantum yields were...initiator. Recrystallisation from ethanol gave colorless plates in 51Z yield . Anal.calcd. for C1 4 Hi 8 Br 2 O5 : C,39.5; H,4.3. Found: C, 39.6; H,4.3Z. 1 H...olive-green product was soxhlet extracted with diethyl ether for 3 days. Benzene recrystallisation provided 2.02g (31Z) of colorless small needles

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

KAUST Repository

Della Sala, Giorgio; Sicignano, Marina; Schettini, Rosaria; De Riccardis, Francesco; Cavallo, Luigi; Minenkov, Yury; Batisse, Chloé ; Hanquet, Gilles; Leroux, Frederic; IZZO, Irene

2017-01-01

diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts

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

International Nuclear Information System (INIS)

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

1995-01-01

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

Persistent organic pollutants in red-crowned cranes (Grus japonensis) from Hokkaido, Japan.

Science.gov (United States)

Kakimoto, Kensaku; Akutsu, Kazuhiko; Nagayoshi, Haruna; Konishi, Yoshimasa; Kajimura, Keiji; Tsukue, Naomi; Yoshino, Tomoo; Matsumoto, Fumio; Nakano, Takeshi; Tang, Ning; Hayakawa, Kazuichi; Toriba, Akira

2018-01-01

The red-crowned crane (Grus japonensis) from eastern Hokkaido is classified as a Special Natural Monument in Japan. In this study, we determined the concentrations of persistent organic pollutants (POPs) in red-crowned crane muscle tissues (n = 47). Polychlorinated biphenyls (PCBs) had the highest median concentration (240ng/g lipid weight), followed by dichlorodiphenyltrichloroethane and its metabolites (DDTs) (150ng/g lipid weight), chlordane-related compounds (CHLs) (36ng/g lipid weight), hexachlorobenzene (HCB) (16ng/g lipid weight), hexachlorocyclohexanes (HCHs) (4.4ng/g lipid weight), polybrominated diphenyl ethers (PBDEs) (1.8ng/g lipid weight), and finally, Mirex (1.5ng/g lipid weight). Additionally, a positive correlation was found among POP concentrations. No sex differences beyond body parameters were observed. Additionally, red-crowned cranes exhibited a high enantiomeric excess of (+)-alpha-HCH, with enantiomer fractions varying from 0.51 to 0.87 (average: 0.69). Copyright © 2017 Elsevier Inc. All rights reserved.

Polyether complexes of groups 13 and 14.

Science.gov (United States)

Swidan, Ala'aeddeen; Macdonald, Charles L B

2016-07-21

Notable aspects of the chemistry of complexes of polyether ligands including crown ethers, cryptands, glycols, glymes, and related polyether ligands with heavier group 13 and 14 elements are reviewed with a focus on results from 2005 to the present. The majority of reported polyether complexes contain lead(ii) and thallium(i) but recent breakthroughs in regard to the preparation of low oxidation state reagents of the lighter congeners have allowed for the generation of complexes containing indium(i), gallium(i), germanium(ii), and even silicon(ii). The important roles of ligand size, donor types, and counter anions in regard to the chemical properties of the polyether complexes is highlighted. A particular focus on the structural aspects of the numerous coordination complexes provides a rationale for some of the spectacular contributions that such compounds have made to Modern Main Group Chemistry.

Effects of crown ethers in nanocomposite silica-gel electrolytes on the performance of quasi-solid-state dye-sensitized solar cells

KAUST Repository

Huang, Kuan-Chieh; Vittal, R.; Ho, Kuo-Chuan

2010-01-01

I) and iodine (I2) in 3-methoxypropionitrile (MPN) solvent. Three types of CEs, 12-crown-4 (12-C-4), 15-crown-5 (15-C-5), and 18-crown-6 (18-C-6) were used as additives to the gel electrolytes. DSSCs containing CEs showed enhancements in solar

Developmental toxicity of diphenyl ether herbicides in nestling American kestrels.

Science.gov (United States)

Hoffman, D J; Spann, J W; LeCaptain, L J; Bunck, C M; Rattner, B A

1991-11-01

Beginning the day after hatching, American kestrel (Falco sparverius) nestlings were orally dosed for 10 consecutive days with 5 microliters/g of corn oil (controls) or one of the diphenyl ether herbicides (nitrofen, bifenox, or oxyfluorfen) at concentrations of 10, 50, 250, or 500 mg/kg in corn oil. At 500 mg/kg, nitrofen resulted in complete nestling mortality, bifenox in high (66%) mortality, and oxyfluorfen in no mortality. Nitrofen at 250 mg/kg reduced nestling growth as reflected by decreased body weight, crown-rump length, and bone lengths including humerus, radius-ulna, femur, and tibiotarsus. Bifenox at 250 mg/kg had less effect on growth than nitrofen, but crown-rump, humerus, radius-ulna, and femur were significantly shorter than controls. Liver weight as a percent of body weight increased with 50 and 250 mg/kg nitrofen. Other manifestations of impending hepatotoxicity following nitrofen ingestion included increased hepatic GSH peroxidase activity in all nitrofen-treated groups, and increased plasma enzyme activities for ALT, AST, and LDH-L in the 250-mg/kg group. Bifenox ingestion resulted in increased hepatic GSH peroxidase activity in the 50- and 250-mg/kg groups. Nitrofen exposure also resulted in an increase in total plasma thyroxine (T4) concentration. These findings suggest that altricial nestlings are more sensitive to diphenyl ether herbicides than young or adult birds of precocial species.

Membrane and Films Based on Novel Crown-Containing Dyes as Promising Chemosensoring Materials

Directory of Open Access Journals (Sweden)

Sergei Yu. Zaitsev

2010-12-01

Full Text Available This paper discusses several works on supramolecular systems such as monolayer and multilayer, polymer films of various crown-containing dyes, surface-active monomers and polymers. Design, production and investigation of the membrane nanostructures based on crown ethers is a rapidly developing field at the “junction” of materials sciences and nanotechnology. These nanostructures can serve as convenient models for studying the self-organization and molecular recognition processes at interfaces that are typical for biomembranes. Based on the results obtained for such structures by absorption and fluorescence spectroscopy, atomic force and Brewster-angle microscopy, surface pressure and surface potential isotherm measurements, the possibility of developing micro- and nanomaterials possessing a set of specified properties (including chemosensor, photochromic and photorefractive materials is demonstrated.

A new PVC based membrane sensor of dibenzo-18-crown-6 for strontium

International Nuclear Information System (INIS)

Singh, Ashok K.; Bhattacharjee, G.; Baniwal, Seema; Singh, Manendra

1999-01-01

Dibenzo-18-crown-6 crown ether is found to exhibit quite promising selectivity for Sr 2+ ions. It can be used to estimate strontium in the range 5.0 x 10 -6 to 1.0 x 10 -1 mol dm -3 (0.28 to 8.76 x 10 -3 mg dm -3 ) with a near-Nernstian slope of 28 mV per decade of concentration. The working pH range of the proposed sensor is 2.0-6.0 with a response time of 25 s. The sensor can be used for more than three months in aqueous as well as in partially non-aqueous media. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergent matter. (author)

Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether

Energy Technology Data Exchange (ETDEWEB)

Boda, Łukasz, E-mail: lboda@chemia.uj.edu.pl; Boczar, Marek; Gług, Maciej; Wójcik, Marek J. [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland)

2015-11-28

Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl–H and Cl–D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl–H and Cl–D stretching bands were performed and the results were compared with experimental spectra.

Antibiotic Potency against E. coli Is Enhanced by Channel-Forming Alkyl Lariat Ethers.

Science.gov (United States)

Negin, Saeedeh; Patel, Mohit B; Gokel, Michael R; Meisel, Joseph W; Gokel, George W

2016-11-17

Several N,N'-bis(n-alkyl-4,13-diaza[18]crown-6) lariat ethers were found to significantly enhance the potency of rifampicin and tetracycline, but not erythromycin and kanamycin, against the non-pathogenic DH5α and K-12 strains of Escherichia coli when administered at levels below their minimum inhibitory concentrations (MICs). The enhancements in antibiotic potency observed for the lariat ethers ranged from three- to 20-fold, depending on the strain of E. coli, the antibiotic, and the lengths of the alkyl chains attached at the macroring nitrogen atoms. The dialkyl lariat ethers, previously thought to only be cation carriers, formed well-behaved, ion-conducting pores in soybean asolectin membranes, as judged by planar bilayer conductance measurements. The ability of lariat ethers to form stable pores, which appeared to be aggregated, depended in part on alkyl chain length and in part on the composition of the bilayer membrane in which they were studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of road soil cement compositions modified with complex additive based on polycarboxylic ether

Science.gov (United States)

Bulanov, P. E.; Vdovin, E. A.; Mavliev, L. F.; Kuznetsov, D. A.

2018-03-01

The paper is focused on the research results of the main physical and technical properties of the cement-stabilized polymineral clay modified with a complex hydrophobic plasticizer based on polycarboxylate and octyltriethoxysilane ethers. A graphical result interpretation of the mathematic model which shows the influence of the complex hydrophobic plasticizer components on the cement-stabilized polymineral clay, containing more than 85% of relict minerals, has been designed. The research significance for the building sector lies in the fact that applying a complex hydrophobic plasticizer provides increasing the compressive strength of the cement-stabilized polymineral clay up to 102%, the tensile bending strength – up to 88%, the freeze-thaw resistance – up to 114%.

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

Energy Technology Data Exchange (ETDEWEB)

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

1978-01-01

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

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

International Nuclear Information System (INIS)

Clearfield, Abraham

2003-01-01

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

Crystalline diuranium phosphinidiide and μ-phosphido complexes with symmetric and asymmetric UPU cores

Energy Technology Data Exchange (ETDEWEB)

Rookes, Thomas M.; Gardner, Benedict M.; Gregson, Matthew; Tuna, Floriana; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester, Manchester (United Kingdom); Balazs, Gabor; Scheer, Manfred [Institute of Inorganic Chemistry, University of Regensburg (Germany)

2017-08-21

Reaction of [U(Tren{sup TIPS})(PH{sub 2})] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiPr{sup i}{sub 3}){sub 3}) with C{sub 6}H{sub 5}CH{sub 2}K and [U(Tren{sup TIPS})(THF)][BPh{sub 4}] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren"T"I"P"S)}{sub 2}(μ-PH)] (3). Treatment of 3 with C{sub 6}H{sub 5}CH{sub 2}K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium μ-phosphido complex [{U(Tren"T"I"P"S)}{sub 2}(μ-P)][K(B15C5){sub 2}] (4). Alternatively, reaction of [U(Tren{sup TIPS})(PH)][Na(12C4){sub 2}] (5, 12C4=12-crown-4 ether) with [U{N(CH_2CH_2NSiMe_2Bu"t)_2CH_2CH_2NSi(Me)(CH_2)(Bu"t)}] (6) produced the diuranium μ-phosphido complex [{U(Tren"T"I"P"S)}(μ-P){U(Tren"D"M"B"S)}][Na(12C4){sub 2}] [7, Tren{sup DMBS}=N(CH{sub 2}CH{sub 2}NSiMe{sub 2}Bu{sup t}){sub 3}]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

NMR study of rare earth and actinide complexes

International Nuclear Information System (INIS)

Villardi de Montlaur de, G.C.

1978-01-01

Proton magnetic resonance studies of lanthanide shift reagents with olefin-transition metal complexes, monoamines and diamines as substrates are described. Shift reagents for olefins are reported: Lnsup(III)(fod) 3 can induce substantial shifts in the nmr spectra of a variety of olefins when silver 1-heptafluororobutyrate is used to complex the olefin. The preparation, properties and efficiency of such systems are described. Configurational aspects and exchange processes of Lnsup(III)(fod) 3 complexes with secondary and tertiary monoamines are analysed by means of dynamic nmr. Factors influencing the stability and the stoichiometry of these complexes and various processes such as nitrogen inversion and ligand exchange are discussed. At low temperature, ring inversion can be slow on an nmr time-scale for Lnsup(III)(fod) 3 -diamino chelates. Barriers to ring inversion in substituted ethylenediamines and propanediamines are obtained. Steric factors appear to play an important role in the stability and kinetics of these bidentate species. The synthesis of uranium-IV crown-ether and cryptate complexes is described. A conformational study of these compounds show evidence of an insertion of the paramagnetic cation as witnessed by the large induced shifts observed. The insertion of uranium in the macrocyclic ligand of a UCl 4 -dicyclohexyl-18-crown-6 complex is confirmed by an X-ray structural determination [fr

Coprecipitation of trace amounts of 137Cs and 85Sr with [Na(18-Crown-6]BPh4 from neutral and alkaline solutions

International Nuclear Information System (INIS)

Kulyukhin, S.A.; Konovalova, N.A.; Rumer, I.A.; Kamenskaya, A.N.; Mikheev, N.B.

2005-01-01

Coprecipitation of 137 Cs and 85 Sr with [Na(18-crown-6]BPh 4 solid phase from aqueous, aqueous-ethanolic, and alkaline solutions is studied. 137 C s and 85 Sr co-crystallize with [Na(18-crown-6]BPh 4 from aqueous and aqueous-ethanolic solutions. The cocrystallization coefficients D of 137 Cs and 85 Sr from aqueous solutions are 2.6 ± 0.5 and 3.3 ± 0.3, respectively. For aqueous-ethanolic solutions, the corresponding values are 4.4 ± 0.5 and 3.4 ± 0.4. In the alkaline solutions (0.1 and 1 M NaOH), 54-74% of 137 Cs and 37-51% of 85 Sr pass into the [Na(18-crown-6)]BPh 4 solid phase, depending on the crown ether concentration in the system [ru

Synthesis and spectroscopic characterization of Y-shaped fluorophores with an imidazole core containing crown ether moieties

Energy Technology Data Exchange (ETDEWEB)

Doğru, Ümit; Öztürk Ürüt, Gülsiye, E-mail: gulsiye.ozturk@deu.edu.tr; Bayramin, Dilek

2015-07-15

In this study three new Y-shaped fluorophores, 4,5-(2,2'-diphenyl)vinyl-{2-[(1,4,7,10-tetraoxa-13-azacyclopentadecyl) phenyl]}-1H-imidazole (1a), 4,5-{[2,2'-bis(4-methoxyphenyl)vinyl]-[2-(1,4,7,10-tetraoxa-13- azacyclopentadecyl)-phenyl]}-1H-imidazole (1b) and 4,5-(2,2'-diphenyl)vinyl-{2-(1,4,7,10,13-benzopentaoxacyclopentadecyl)} -1H-imidazole (1c) were synthesized. 1,6-Diphenylhexa-1,5-diene-3,4-dione (2a) and 1,6-bis(4-methoxyphenyl)hexa-1,5-diene-3,4-dione (2b) were synthesized as preliminary fluorophores and then reacted with 4-formylbenzo-aza-15-crown-5 (3a) and 4-formylbenzo-15-crown-5 (3b) to obtain the three Y-shaped fluorophores 1a, 1b and 1c. 4-formylbenzo-aza-15-crown-5 and 4-formylbenzo-15-crown-5 intermediates were synthesized with Vilsmeier–Haack reaction. The photophysical properties such as maximum absorption wavelengths, maximum emission wavelengths, Stokes' shifts, singlet energies, fluorescence quantum yields and photostabilities of the compounds were investigated by measuring absorption and emission spectra in a series of solvents of varying polarities of toluene (TOL), dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EA), acetonitrile (ACN), and N,N-dimethylformamide (DMF). The three compounds 1a, 1b and 1c exhibited emission maxima in the 412–677 nm range. All the derivatives synthesized exhibited excellent photostability in all the solvents tested. - Highlights: • Three new Y-shaped fluorophores were synthesized for the first time. • Their absorption and emission properties were investigated. • All the derivatives synthesized exhibited excellent photostability.

Synthesis and spectroscopic characterization of Y-shaped fluorophores with an imidazole core containing crown ether moieties

International Nuclear Information System (INIS)

Doğru, Ümit; Öztürk Ürüt, Gülsiye; Bayramin, Dilek

2015-01-01

In this study three new Y-shaped fluorophores, 4,5-(2,2'-diphenyl)vinyl-{2-[(1,4,7,10-tetraoxa-13-azacyclopentadecyl) phenyl]}-1H-imidazole (1a), 4,5-{[2,2'-bis(4-methoxyphenyl)vinyl]-[2-(1,4,7,10-tetraoxa-13- azacyclopentadecyl)-phenyl]}-1H-imidazole (1b) and 4,5-(2,2'-diphenyl)vinyl-{2-(1,4,7,10,13-benzopentaoxacyclopentadecyl)} -1H-imidazole (1c) were synthesized. 1,6-Diphenylhexa-1,5-diene-3,4-dione (2a) and 1,6-bis(4-methoxyphenyl)hexa-1,5-diene-3,4-dione (2b) were synthesized as preliminary fluorophores and then reacted with 4-formylbenzo-aza-15-crown-5 (3a) and 4-formylbenzo-15-crown-5 (3b) to obtain the three Y-shaped fluorophores 1a, 1b and 1c. 4-formylbenzo-aza-15-crown-5 and 4-formylbenzo-15-crown-5 intermediates were synthesized with Vilsmeier–Haack reaction. The photophysical properties such as maximum absorption wavelengths, maximum emission wavelengths, Stokes' shifts, singlet energies, fluorescence quantum yields and photostabilities of the compounds were investigated by measuring absorption and emission spectra in a series of solvents of varying polarities of toluene (TOL), dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EA), acetonitrile (ACN), and N,N-dimethylformamide (DMF). The three compounds 1a, 1b and 1c exhibited emission maxima in the 412–677 nm range. All the derivatives synthesized exhibited excellent photostability in all the solvents tested. - Highlights: • Three new Y-shaped fluorophores were synthesized for the first time. • Their absorption and emission properties were investigated. • All the derivatives synthesized exhibited excellent photostability

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”

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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.)

Electroactive crown ester-Cu2+ complex with in-situ modification at molecular beacon probe serving as a facile electrochemical DNA biosensor for the detection of CaMV 35s.

Science.gov (United States)

Zhan, Fengping; Liao, Xiaolei; Gao, Feng; Qiu, Weiwei; Wang, Qingxiang

2017-06-15

A novel electrochemical DNA biosensor has been facilely constructed by in-situ assembly of electroactive 4'-aminobenzo-18-crown-6-copper(II) complex (AbC-Cu 2+ ) on the free terminal of the hairpin-structured molecule beacon. The 3'-SH modified molecule beacon probe was first immobilized on the gold electrode (AuE) surface through self-assembly chemistry of Au-S bond. Then the crow ester of AbC was covalently coupled with 5'-COOH on the molecule beacon, and served as a platform to attach the Cu 2+ by coordination with ether bond (-O-) of the crown cycle. Thus, an electroactive molecule beacon-based biosensing interface was constructed. In comparison with conventional methods for preparation of electroactive molecule beacon, the approach presented in this work is much simpler, reagent- and labor-saving. Selectivity study shows that the in-situ fabricated electroactive molecule beacon remains excellent recognition ability of pristine molecule beacon probe to well differentiate various DNA fragments. The target DNA can be quantatively determined over the range from 0.10pM to 0.50nM. The detection limit of 0.060pM was estimated based on signal-to-noise ratio of 3. When the biosensor was applied for the detection cauliflower mosaic virus 35s (CaMV 35s) in soybean extraction samples, satisfactory results are achieved. This work opens a new strategy for facilely fabricating electrochemical sensing interface, which also shows great potential in aptasensor and immurosensor fabrication. Copyright © 2016 Elsevier B.V. All rights reserved.

PREPARATION AND PROPERTIES OF THREE NEUTRAL COPPER (I COMPLEXES BASED ON BIS[2-(DIPHENYLPHOSPHINOPHENYL]ETHER PHENYL] ETHER AND SUBSTITUTED IMIDAZOLE-2,9-DIMETHYL-1,10-PHENANTHROLINE

Directory of Open Access Journals (Sweden)

Xin Fang Liu

2017-10-01

Full Text Available With deprotonated 2-(4-nitro phenyl-, 2-(4-methyl phenyl-, and 2-(4-methoxy phenyl imidazoled-2,9-dimethyl-1,10-phenanthroline (NPIP, MPIP and MoPIP as nitrogen ligands, as well as bis[2-(diphenylphosphino phenyl]ether (DPEphos as phosphorus ligand, three Cu(I neutral complex has been synthesized and characterized by infrared spectroscopy (IR, elemental analysis and 1H NMR methods. TG-DTA shows that the complex begins to decompose when the temperature reached about 220 oC, indicating their high thermo-stability. The emission spectrum shows that the complexes exhibit yellow emission with a peak emission wavelength of 576, 585 and 596 nm under excitation of 287 nm in powder state.

Absorption and biotransformation of polybrominated diphenyl ethers DE-71 and DE-79 in chicken (Gallus gallus), mallard (Anas platyrhynchos), American kestrel (Falco sparverius) and black-crowned night-heron (Nycticorax nycticorax) eggs

Science.gov (United States)

McKernan, Moira A.; Rattner, Barnett A.; Hatfield, Jeff S.; Hale, Robert C.; Ottinger, Mary Ann

2010-01-01

We recently reported that air cell administration of penta-brominated diphenyl ether (penta-BDE; DE-71) evokes biochemical and immunologic effects in chicken (Gallus gallus) embryos at very low doses, and impairs pipping (i.e., stage immediately prior to hatching) and hatching success at 1.8 ug g-1 egg (actual dose absorbed) in American kestrels (Falco sparverius). I n the present study, absorption of polybrominated diphenyl ether (PBDE) congeners was measured following air cell administration of a penta-BDE mixture (11.1 ug DE-71 g-1 egg) or an octa-brominated diphenyl ether mixture (octa-BDE; DE-79; 15.4 ug DE-79 g-1 egg). Uptake of PBDE congeners was measured at 24 h post-injection, midway through incubation, and at pipping in chicken, mallard (Anas platyrhynchos), and American kestrel egg contents, and at the end of incubation in black-crowned night-heron (Nycticorax nycticorax) egg contents. Absorption of penta-BDE and octa-BDE from the air cell into egg contents occurred throughout incubation; at pipping, up to 29.6% of penta-BDE was absorbed, but only 1.40-6.48% of octa-BDE was absorbed. Higher brominated congeners appeared to be absorbed more slowly than lower brominated congeners, and uptake rate was inversely proportional to the log Kow of predominant BDE congeners. Six congeners or co-eluting pairs of congeners were detected in penta-BDE-treated eggs that were not found in the dosing solution suggesting debromination in the developing embryo, extraembryonic membranes, and possibly even in the air cell membrane. This study demonstrates the importance of determining the fraction of xenobiotic absorbed into the egg following air cell administration for estimation of the lowest-observed-effect level.

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...

Study on the application of crown ether for neutron activation analysis of rubidium and rhenium in rock samples

International Nuclear Information System (INIS)

Wang Xiaolin; Fu Yibei; Liu Yinong; Xiong Zonghua; Hao Fanhua

1996-01-01

The extraction behaviour of rubidium and rhenium with 18-crown-6 (18C6) and benzo-15-crown-5 (B15C5) in nitrobenzene from picric acid or potassium hydroxide solution are studied and methods for separation and determination are developed. The molar ratio of 18C6 to Rb and B15C5 to Re in the extracted species is probably 2:1. Rubidium and rhenium in rock samples are satisfactorily determined by neutron activation method

The influence of constitutional isomerism and change on molecular recognition processes.

Science.gov (United States)

Williams, Avril R; Northrop, Brian H; Houk, Kendall N; Stoddart, J Fraser; Williams, David J

2004-10-25

Three constitutionally isomeric bis(naphthylmethyl)ammonium ions, in which the two naphthyl groups are substituted 1) both at their 1-positions, 2) one at its 1-position and the other at its 2-position, and 3) both at their 2-positions, have been investigated separately in solution for their propensities to undergo spontaneous self-assembly with three different [24]crown-8 derivatives, namely, pyrido[24]crown-8 (P24C8), dipyrido[24]crown-8 (DP24C8) and dibenzo[24]crown-8 (DB24C8), in turn to form [2]pseudorotaxanes. The strengths of the 1:1 complexes depend on the composition of the secondary dialkylammonium ions and on the nature of the crown ether hosts; generally, as far as the guest cation is concerned, the 1/1- and 2/2-isomers form stronger complexes, as indicated by stability constant measurements, than the 1/2-isomer and, as far as the crown ethers are concerned, the more flexible P24C8 is a much more efficient host than either DP24C8 or DB24C8. The rates of formation of the [2]pseudorotaxanes are fast (i.e., taking no more than a few minutes) in solution with the exception of one case, that is, in which the crown ether host is DB24C8 and the guest cation is the 1/1-isomer, when it can take upwards of one month for the complexation-decomplexation equilibrium to be established at room temperature. In all cases, the equilibrium between complexed and uncomplexed species is slow on the NMR timescale, allowing the determination of stability constants to be made readily using the single-point method. X-ray crystallography and molecular modeling have been used to gain insight into ground and transition state interactions, respectively, in some of the [2]pseudorotaxanes. The relative stabilities of the three [2]pseudorotaxanes formed by each guest cation in the presence of the three crown ether hosts were also evaluated in solution by competition experiments that were monitored by (1)H NMR spectroscopy. By and large the results of the competition experiments could

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

Extraction of Eu(III) by dinonylnaphthalenesulfonic acid and synergistic effects of crown ethers and trioctylphosphine oxide

International Nuclear Information System (INIS)

Ramadan, A.; Khalifa, S.M.; Mahmoud, M.; Souka, N.

1993-01-01

The extraction of Eu(III) by dinonylnaphthalenesulfonic acid (HDNNS) in benzene from nitrate and perchlorate solutions has been investigated. For nitrate solutions the ionic strength of the aqueous phase was kept constant at 0.1M using NaNO 3 -HNO 3 mixtures. The Eu distribution was measured at different temperatures. The following stoichiometric formulae for the Eu species in benzene were derived: Eu(NO 3 )(H n-1 (DNNS) n ) 2 and Eu(H n-1 (DNNS) n )3, from the nitrate and perchlorate medium respectively (n being a small number, e.g. 1,2 or 3). The equilibrium constants were calculated and the thermodynamic parameters of the system were determined. When adding dibenzo-24-crown-8, dicyclohexyl-18-crown-6 or trioctylphosphine oxide, no synergism, but rather antagonism was observed. (author) 14 refs.; 8 figs.; 2 tabs

Uranium complexes with macrosyclic polyethers. Synthesis and structural chemical analysis

International Nuclear Information System (INIS)

Elbasyouny, A.

1983-01-01

This dissertation reports about studies on the chemical coordination behaviour of uranium of oxidation stages IV and VI with regard to twelve different macrocyclic ligands. For the preparation of the complexes, for every system a different method has been developed. The elementary analysis of the various complexes including the uranium had been done by X-ray fluorescence analysis, and the structural characterization proceeded via vibrational, uv-vis and emission spectroscopy as well as 1 H-NMR and 13 C-spin-lattice relaxation time studies. Conformational analysis of the polyethers used allowed the structural changes in the complexes to be observed. The structural analysis of the hydrous uranium VI crown ether complexes yielded information of characteristic features of these types of complexes. The first coordination sphere of the uranyl ion with covalently bonded anion remains unchanged. As to the water content, there is a certain range. Depending upon the solvent used, the complexes have two or four H 2 O molecules per formula unit. (orig./EF) [de

Hardness and wear properties of boron-implanted poly(ether-ether-ketone) and poly-ether-imide

International Nuclear Information System (INIS)

Lee Youngchul; Lee, E.H.; Mansur, L.K.

1992-01-01

The effects of boron beam irradiation on the hardness, friction, and wear of polymer surfaces were investigated. Typical high-performance thermoplastics, poly(ether-ether-ketone) (PEEK) and a poly-ether-imide (Ultem) were studied after 200 keV boron ion beam treatment at ambient temperature to doses of 2.3x10 14 , 6.8x10 14 , and 2.2x10 15 ions cm -2 . The hardnesses of pristine and boron-implanted materials were characterized by a conventional Knoop method and a load-depth sensing nanoindentation technique. Both measurements showed a significant increase in hardness with increasing dose. The increase in hardness was also found to depend on the penetration depth of the diamond indenter. Wear and friction properties were characterized by a reciprocating sliding friction tester with an SAE 52100 high-carbon, chrome steel ball at 0.5 and 1 N normal loads. Wear and frictional properties varied in a complex fashion with polymer type and dose, but not much with normal load. A substantial reduction in friction coefficient was observed for PEEK at the highest dose but no reduction was observed for Ultem. The wear damage was substantially reduced at the highest dose for both Ultem and PEEK. For the system studied, the highest dose, 2.2x10 15 ions cm -2 , appears to be optimum in improving wear resistance for both PEEK and Ultem. (orig.)

Properties of solvated electrons, alkali anions and other species in metal solutions and kinetics of cation and electron exchange reactions. Final report

International Nuclear Information System (INIS)

Dye, J.L.

1979-01-01

The properties of solutions of alkali metals in amine solvents were studied by optical, ETR, NMR and electrochemical methods. Complexation of the alkali cations by crown ethers and cryptands permitted the preparation of concentrated solutions of alkali metals in amine and ether solvents. Extensive alkali metal NMR studies of the exchange of M + with crown-ethers and cryptands and of the alkali metal anion, M - , were made. The first crystalline salt of an alkali metal anion, Na + Cryptand [2.2.2]Na - was synthesized and characterized and led to the preparation of other alkali metal anion salts. This research provided the foundation for continuing studies of crystalline alkalide salts

Crystal structures of two solvates of (18-crown-6potassium acetate

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Phil Liebing

2016-12-01

Full Text Available The crystal and molecular strutures of two solvated forms of [K(18c6]OAc (18c6 = 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane and OAc = acetate were determined by single-crystal X-ray diffraction, namely (acetato-κ2O,O′(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium dihydrate, [K(CH3COO(C12H24O6]·2H2O (1 and (acetato-κ2O,O′aqua(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium acetic acid monosolvate [K(CH3COO(C12H24O6(H2O]·CH3COOH (2. In both compounds, the acetate anion is bonded to the potassium ion in a chelating fashion and the metal atom is consequently slightly displaced from the O6 plane of the crown ether. In the crystals, O—H...O hydrogen bonds lead to a polymeric ladder structure in the dihydrate 1, while the acetic acid hydrate 2 features inversion dimers.

Developing of Ytrium-90 Generator Based on Extraction Chromatography with Crown Ether

International Nuclear Information System (INIS)

Yassine, T.; Mukhallalati, Ch.H.

2009-01-01

Although the use of radionuclides for therapeutic purposed goes back to about 60 years ago, but interest in this therapy is rapidly increasing in the field of nuclear medicine. The introduction and acceleration of such techniques require the continuous availability and acceptable cost of therapeutic radionuclides and radiopharmaceuticals. Most of therapeutic radionuclides, are reactor (Ho-166, Lu-177 Sm-153, I-131...). Produced ones which makes the generator produced radionuclides such Y-90, is more convenient to start with for developing therapeutic radiopharmaceutical in countries where there are no reactor. Ytrium-90 is an important radionuclide for radioimmunotherapeutic and for radiosynviorethesis. It is pure single high energy beta emitter (Ep=2.3 Mev), decaying to stable Zirconium-90 with half-life of about 64 hrs. It is availability, as generator products resulting from the decay of the long lived strontium-90 (T1/2 = 28y) has increased its importance in nuclear medicine and accelerated its applications. The AECS has initiated wide Programme for development and production of radiopharmaceuticals for covering local and regional demands of nuclear medicine. Existed facility including Cyclotron (cyclon 30 IBA), technetium-99m generator and kits production lines and iodine-131 dispensing and labeling plant, needs to be enhanced by more therapeutic products. The absence of nuclear reactor for radionuclide production makes the generator technology to be a convenient choice. Therefore, Ytrium-90 radiopharmaceuticals were targeted and 90Sr/90Y generator was developed for these purposes. Several designs of Ytrium-90 generator were developed according to different separation techniques, such as solvent extraction, ion exchange, supported liquid membrane and electrodeposition, and each has deferent characterizations and Performances. We found that extraction Chromatography by 18C6 Crown ether loaded on Teflon resins (Sr-Spec) is very convenient for Production of ultra

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

Polycation-sodium lauryl ether sulfate-type surfactant complexes: influence of ethylene oxide length.

Science.gov (United States)

Vleugels, Leo F W; Pollet, Jennifer; Tuinier, Remco

2015-05-21

Polyelectrolyte-surfactant complexes (PESC) are a class of materials which form spontaneously by self-assembly driven by electrostatic and hydrophobic interactions. PESC containing sodium lauryl ether sulfates (SLES) have found wide application in hair care products like shampoo. Typically, SLES with only one or two ethylene oxide (EO) groups are used for this application. We have studied the influence of the size of the EO block (ranging from 0 to 30 EO groups) on complexation with two model polycations: linear polyDADMAC and branched PEI. PESC size and electrostatic properties were determined during stepwise titration of buffered polycation solutions. The critical aggregation concentration (CAC) of PESC was determined by surface tension measurements and fluorescence spectroscopy. For polyDADMAC, there is no influence of the size of the EO block on the complexation behavior; the stiff polycation governs the structure formation. For PEI, it was seen that the EO block size does affect the structure of the complexes. The CAC value of the investigated complexes turns out to be rather independent of the EO block size; however, the CMC/CAC ratio decreases with increasing size of the EO block. This latter observation explains why the Lochhead-Goddard effect is most effective for small EO blocks.

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.

Solvent extraction of technetium from alkaline waste media using bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6

International Nuclear Information System (INIS)

Bonnesen, P.V.; Presley, D.J.; Moyer, B.A.

1995-01-01

The crown ether bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 can be utilized in a solvent-extraction process for the removal of technetium as pertechnetate ion, TcO 4 - from solutions simulating highly radioactive alkaline defense wastes (''tank wastes'') stored at several sites in the United States. The process employs non-halogenated and non-volatile diluents and modifiers and includes an efficient stripping procedure using only water. More than 95% of the pertechnetate present at 6 x 10 -5 M in Melton Valley (Oak Ridge, TN) and Hanford (Washington) tank-waste simulants was removed following two cross-current extraction contacts using 0.02 M bis-4,4'(5')[(tertbutyl)cyclohexano]- 18-crown-6 in 2:1 vol/vol TBP/Isopar reg-sign M diluent at 25 C. Similarly, for both simulants, more than 98% of the pertechnetate contained in the solvent was back-extracted following two cross-current stripping contacts using deionized water

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)

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

Studies on the separation of {sup 89}Sr(II) from irradiated yttria target using 4, 4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) by solvent extraction technique

Energy Technology Data Exchange (ETDEWEB)

Saha, Debasish; Vithya, Jayagopal; Kumar, Ramalingam; Venkata Subramani, Canchipuram Ramamoorthy; Vasudeva Rao, Polur Ranga [Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam (India). Chemistry Group

2016-07-01

The radioisotope {sup 89}Sr as {sup 89}SrCl{sub 2} is medically useful for bone pain palliation and is produced in fast reactors using the {sup 89}Y(n, p){sup 89}Sr reaction. A procedure for isolation of the radionuclide {sup 89}Sr by chemical processing of the irradiated Y{sub 2}O{sub 3} target has been standardised and trial runs have been carried out at the Fast Breeder Test Reactor (FBTR), Kalpakkam. The chemical processing of the irradiated Y{sub 2}O{sub 3} target involves (i) the removal of target Y(III) by TBP extraction and (ii) further purification of the separated {sup 89}Sr fraction by cationic exchange chromatography. However a selective isolation of {sup 89}Sr by the Sr-specific crown ether makes the above chemical processing faster and relatively simple. This work presents a study on the selective removal of Sr from the irradiated target dissolver solution using the Sr-specific crown ether 4,4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) in octanol medium. The separation behaviour of the other impurities such as Ce(IV), Y(III), Tb(III), Eu(III), Zn(II), Mn(II) and Rb(I) present along with Sr(II) in the irradiated sample was also investigated. The method of separation by using the crown ether DtBuCH18C6 is proved to be a potential tool for the purification of {sup 89}Sr(II) source produced from yttria target in fast reactors.

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.

Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

Directory of Open Access Journals (Sweden)

Atsushi Morikawa

2016-02-01

Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

Numerical analysis of spray characteristics of dimethyl ether and diethyl ether fuel

International Nuclear Information System (INIS)

Mohan, Balaji; Yang, Wenming; Yu, Wenbin; Tay, Kun Lin

2017-01-01

Highlights: • Thermo-physical properties of liquid DME and DEE are reported. • Ether fuels tend to cavitate higher compared to that of diesel fuel. • Spray tip penetration and SMD are found to be lesser for ether fuels. • Ether fuels shows excellent atomization behavior. - Abstract: In this work, the spray characteristics of ether fuels such as dimethyl ether (DME) and diethyl ether (DEE) have been numerically investigated using KIVA-4 CFD code. A new hybrid spray model developed by coupling the standard KHRT model to cavitation sub model was used. The detailed thermo-physical properties of ether fuels have been predicted and validated with experimental results available from literature. The cavitation inception inside the injector nozzle hole has been studied for ether fuels in comparison with diesel fuel. It was found that ether fuels cavitates higher compared to that of conventional diesel fuel because of its low viscosity. The spray tip penetration of diesel fuel was longer than that of ether fuels due to high viscosity and density of diesel fuel. Ether fuels characterized by low Ohnesorge number and high Reynolds number showed better atomization behavior compared to that of the diesel fuel.

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.

Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Energy Technology Data Exchange (ETDEWEB)

Gardner, Benedict M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Balazs, Gabor; Scheer, Manfred [Institut of Inorganic Chemistry, University of Regensburg (Germany); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

2014-04-22

Reaction of [U(Tren{sup TIPS})(THF)][BPh{sub 4}] (1; Tren{sup TIPS}=N{CH_2CH_2NSi(iPr)_3}{sub 3}) with NaPH{sub 2} afforded the novel f-block terminal parent phosphide complex [U(Tren {sup TIPS})(PH{sub 2})] (2; U-P=2.883(2) Aa). Treatment of 2 with one equivalent of KCH{sub 2}C{sub 6}H{sub 5} and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U(Tren{sup TIPS})(PH)][K(B15C5){sub 2}] (4; U=P=2.613(2) Aa). DFT calculations reveal a polarized-covalent U=P bond with a Mayer bond order of 1.92. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Interpolymer complexses of vinyl ether copolymer with polyacrylic and polymethacrylic acids

Directory of Open Access Journals (Sweden)

E. Shaikhutdinov

2012-03-01

Full Text Available The interactions between macromolecules of copolymers based on vinyl ethers (vinyl ether of monoethanolamine and vinyl buthyl ether and 2-acryloilamido-2-methylpropanesulphonic acid with polyacrylic and polymethacrylic acid and, as well as study the effect of interpolymer interactions in the adsorption of polymers at the aqueous solution-air interface were investigated. The observed synergistic increase in surface activity of macromolecules into polyelectrolyte mixtures explained by the formation of interpolymer complexes polyacid - copolymer.

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.

Uranium (VI) complexing by macrocyclic or chelating ligands in aqueous solutions stability, formation kinetics, polarographic properties

International Nuclear Information System (INIS)

Brighli, M.

1984-07-01

Stability of chelates (with EDTA,N,N ethylenediamine diacetic acid EDDA nitrilotriacetic acid NTA and iminodiacetic acid) of UO 2 2+ and UO 4 species of uranium VI is studied in aqueous solution (NaClO 4 3M at 25 deg celcius). Structure in solution are proposed and discussed for mononuclear species. Only complexing kinetics (formation and acid hydrolysis) of UO 4 with EDDA and NTA are studied by spectrophotometry (other reactions are too fast). Besides UO 2 2+ complexes are formed with crown ethers I5C5 and I8C6 in aqueous solution (TEA ClO 4 M/10 at 25 deg celcius. Complexes are probably stabilized by solvation. Results are confirmed by voltametry and reduction mechanisms of UO 2 2+ and its complexes on mercury drop are proposed. 143 refs [fr

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...

Cosmic Ether

CERN Document Server

Tomaschitz, R

1998-01-01

A prerelativistic approach to particle dynamics is explored in an expanding Robertson-Walker cosmology. The receding galactic background provides a distinguished frame of reference and a unique cosmic time. In this context the relativistic, purely geometric space-time concept is criticized. Physical space is regarded as a permeable medium, the cosmic ether, which effects the world-lines of particles and rays. We study in detail a Robertson-Walker universe with linear expansion factor and negatively curved, open three-space; we choose the permeability tensor of the ether in such a way that the semiclassical approximation is exact. Galactic red-shifts depend on the refractive index of the ether. In the local Minkowskian limit the ether causes a time variation of mass, which scales inversely proportional to cosmic time. In the globally geodesic rest frames of galactic observers the ether manifests itself in an unbounded speed of signal transfer, in bifurcations of world-lines, and in time inversion effects.

Selective decontamination for cesium and strontium in evaporation concentrates from reprocessing plants with crown ethers by transport through supported liquid membranes

International Nuclear Information System (INIS)

Casas i Garcia, J.

1991-01-01

Reprocessing operations lead to the production of radioactive medium activity liquid waste which is treated by evaporation. The concentrates from reprocessing plant evaporators have to be stored in geological storage sites in view of their strong caesium, strontium and actinides activity. These elements, contained in acid and high sodium nitrate content liquid waste, are removed by means of selective extractants, using the supported liquid membrane technique (SLM), which allows them to be stored in surface sites, the actinides and long-life fission products being respectively recycled and concentrated into reduced volumes. The removal of the actinides is done by means of an Octyl N.N Diisobutyl Carbamoyl Methyl Phosphine Oxyde (C.M.P.O.) based liquid membrane, whereas the removal of the caesium and strontium involves crown ethers. Supported liquid membranes (S.L.M.s) have the advantage of implementing very small quantities of extractant, but, they generally have poor stability. The extractant, the diluent and the phase modifier that constitute the organic phase impregnating the membrane play a vital role in SLM stability; the support also affects stability by its nature and geometry. For the extraction of strontium, DtBu 18 C6 enables higher strontium transfer kinetics to be attained than with DC18 C6. As regards caesium, nDec B21 C7 is the most efficient. Unlike strontium, caesium cannot be quantitatively removed, due to the competition of sodium ions in the concentrate. Stable membranes are obtained with DC18 C6 or DtBu18 C6 diluted in alkylbenzene with an added phase modifier such as decanol or isotridecanol. The highest strontium transfer kinetics were obtained with the DC18 C6/hexylbenzene/isotridecanol mixture

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).

Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

International Nuclear Information System (INIS)

Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

2016-01-01

A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

α-Diazo oxime ethers for N-heterocycle synthesis.

Science.gov (United States)

Choi, Subin; Ha, Sujin; Park, Cheol-Min

2017-06-01

This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

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.

Misconceptions about the ether

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Several misconceptions concerning the ether concept and ether models are reviewed and clarified so that the relationship between modern ether theory and orthodox relativity may be better understood. The question of the ether's supposed superfluidity as a concept, and its status in modern physics remains to be answered. (author)

[Early contributions from Erlangen to the theory and practice of ether and chloroform anesthesia. 1. Heyfelder's clinical trial with ether and chloroform].

Science.gov (United States)

Hintzenstern, U v; Schwarz, W

1996-02-01

The era of modern anaesthesia in Germany began on January 24th, 1847. This day, professor in ordinary Johann Ferdinand Heyfelder anaesthetized a patient with sulphuric ether in the clinic of surgery and ophthalmology of the University of Erlangen. By March 17th, 1847, Heyfelder had performed 121 surgical procedures under ether. The operations in majority were teeth-extractions, and a few more complex operations such as the treatment of a harelip or of lip cancer or the resection of the shoulder joint. Heyfelder described in detail 108 of these inhalations in a little book entitled The experiments with sulphuric ether. This monograph published in March, 1847, represents one of the first complete dissertations on sulphuric ether in the German literature. In a special chapter he analyzed the development of various physiological and psychological parameters during etherization. Heyfelder also examined blood and urine of some etherized patients and reported that he did not find any important or specific alterations. In 1847, Heyfelder was probably the first to apply salt-ether in man. After 4 administrations he concluded that salt ether acted more quickly but shorter than sulphuric ether. Advantageous were its application without problems and ease of induction. Disadvantageous were its high volatility, its price and the difficulty of getting it in a pure form. From December, 1847, on Heyfelder started to use chloroform. He was now able to perform more major operations, for example, the total resection of the hip-joint. In his book The experiments with sulphuric ether, salt ether, and chloroform he describes a great number of anaesthetic administrations using these 3 agents. In his summary Heyfelder concluded, that chloroform was undoubtly superior to sulphuric ether mainly because it was a quicker acting and longer lasting agent and leads to deeper narcosis. Moreover its application was much easier for it needed no special apparatus. However, because of its great

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.

Synthesis and Supramolecular Chemistry of Novel Liquid Crystalline Crown Ether-Substituted Phthalocyanines : Toward Molecular Wires and Molecular Ionoelectronics

NARCIS (Netherlands)

Nostrum, Cornelus F. van; Picken, Stephen J.; Schouten, Arend-Jan; Nolte, Roeland J.M.

1995-01-01

The synthesis of the metal-free and the dihydroxysilicon derivatives of tetrakis[4’,5’-bis(decoxy)benzo-18-crown-6]phthalocyanine is described. The metal-free phthalocyanine is liquid crystalline and exhibits a crystalline phase to mesophase transition at 148 °C. The structures of the crystalline

Selective decontamination of cesium and strontium from evaporation concentrates of spent fuel reprocessing plants with crown ethers by transport through supported liquid membranes

International Nuclear Information System (INIS)

Casas i Garcia, J.

1993-01-01

Reprocessing operations lead to the production of radioactive medium activity liquid waste which is treated by evaporation and solutions of very high salinity are thus formed. The concentrates from reprocessing plant evaporators have to be stored in geological storage sites in view of their strong caesium, strontium and actinides activity. These elements, contained in acid and high sodium nitrate content liquid waste, are removed by means of selective extractants, using the supported liquid membrane technique (SLM), which allows them to be stored in surface sites, the actinides and long-life fission products being respectively recycled and concentrated into reduced volumes. The removal of the actinides is done by means of an Octyl N.N Diisobutyl Carbamoyl Methyl Phosphine Oxide (C.M.P.O.) based liquid membrane, whereas the removal of the caesium and strontium involves crown ethers. Supported liquid membranes (S.L.M.s) have the advantage of implementing very small quantities of extractant, but they generally have poor stability. The extractant, the diluent and the phase modifier impregnating the membrane play a vital role in SLM stability; the support also affects stability by its nature and geometry. For the extraction of strontium, the most lipophilic extractant, DtBu 18 C 6, enables higher strontium transfer kinetics to be attained. As regards caesium, the extremely lipophilic nDec B21 C7 is the most efficient. Caesium cannot be quantitatively removed, due to the competition of the very high content of sodium ions in the concentrate. Stable membranes are obtained with DC18 C6 or DtBu18 C6 diluted in alkylbenzenes with an added phase modifier such as decanol or especially isotridecanol

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

Investigation on silver complexes of novel 1,2,3-triazole linked ...

Indian Academy of Sciences (India)

Abstract. The novel derivatives of 1,2,3-triazole linked crown ethers were investigated towards silver(I) ion coordination. The NMR measurements in deuterated methanol in different ratios of ligand and silver cation were studied. The experiments were performed in order to examine the way of binding Ag(I) ion by the ...

Polynuclear Hydroxido-Bridged Complexes of Platinum(IV) with Terminal Nitrato Ligands.

Science.gov (United States)

Vasilchenko, Danila; Berdugin, Semen; Tkachev, Sergey; Baidina, Iraida; Romanenko, Galina; Gerasko, Olga; Korenev, Sergey

2015-05-18

For the first time the polynuclear hydroxido-bridged platinum(IV) nitrato complexes with nuclearity higher than two were isolated from nitric acid solutions of [Pt(H2O)2(OH)4] and crystallized as supramolecular compounds of macrocyclic cavitands cucurbit[n]uril (CB[n], n = 6,8) and 18-crown-6 ether: [Pt4(μ3-OH)2(μ2-OH)4(NO3)10]·CB[6]·25H2O (I), [Pt6(μ3-OH)4(μ2-OH)6(NO3)12](NO3)2·CB[8]·50H2O (II), and [H3O⊂18-crown-6]2[Pt2(μ2-OH)2(NO3)8][Pt4(μ3-OH)2(μ2-OH)4(NO3)10] (III). The isolation of the compounds in the single crystalline state allows the determination of the structure of the tetranuclear and hexanuclear complexes [Pt4(μ3-OH)2(μ2-OH)4(NO3)10] and [Pt6(μ3-OH)4(μ2-OH)6(NO3)12](2+), which have been previously unknown in the solid state. Stability of Ptx(OH)y cores of the polynuclear nitrato complexes toward alkaline hydrolysis was verified by (195)Pt NMR spectroscopy. Analysis of (195)Pt NMR spectra of the compound III reveals that addition of every Pt(μ-OH)2Pt ring results in ∼260 ppm downfield shift relative to the mononuclear form, which allows the prediction of signal positions for complexes of higher nuclearity.

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.

Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn)

Czech Academy of Sciences Publication Activity Database

Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

2012-01-01

Roč. 26, č. 19 (2012), s. 2287-2294 ISSN 0951-4198 R&D Projects: GA AV ČR IAA400550704 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional support: RVO:61388963 Keywords : pendant crown thioethers * gas-phase * copper (II) complexes * stability constants * ESI-MS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.509, year: 2012

Reproductive toxicity of the glycol ethers.

Science.gov (United States)

Hardin, B D

1983-06-01

The glycol ethers are an important and widely used class of solvents. Recent studies have demonstrated that ethylene glycol monomethyl ether (EGME), ethylene glycol dimethyl ether (EGdiME), ethylene glycol monoethyl ether (EGEE), and ethylene glycol monoethyl ether acetate (EGEEA) are teratogenic. Other studies have demonstrated that testicular atrophy or infertility follow treatment of males with EGME, ethylene glycol monomethyl ether acetate (EGMEA), EGEE, EGEEA, diethylene glycol dimethyl ether (diEGdiME), and diethylene glycol monoethyl ether (diEGEE). Experimental data are reviewed and structure-activity relationships are speculated upon.

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...

Infrared spectra of complex organic molecules in astronomically relevant ice matrices. I. Acetaldehyde, ethanol, and dimethyl ether

Science.gov (United States)

Terwisscha van Scheltinga, J.; Ligterink, N. F. W.; Boogert, A. C. A.; van Dishoeck, E. F.; Linnartz, H.

2018-03-01

Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking. Aim. This work provides infrared reference spectra of acetaldehyde (CH3CHO), ethanol (CH3CH2OH), and dimethyl ether (CH3OCH3) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations. Methods: Fourier transform transmission spectroscopy (500-4000 cm-1/20-2.5 μm, 1.0 cm-1 resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15 K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed. Results: We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 μm bands are recommended, for ethanol the 11.36 and 7.240 μm bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 μm can be used. All spectra are publicly available in the Leiden Database for Ice.

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.

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.

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.

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)).

Selective visual detection of Pb(II) ion via gold nanoparticles coated with a dithiocarbamate-modified 4′-aminobenzo-18-crown-6

International Nuclear Information System (INIS)

Mehta, Vaibhavkumar N.; Kailasa, Suresh Kumar; Solanki, Jignasa N.

2014-01-01

We have developed a crown ether based selective colorimetric sensing scheme for the determination of Pb(II) ion by using gold nanoparticles modified with dithiocarbamate derivative of 4′-aminobenzo-18-crown-6 that acts as a colorimetric probe. Monodisperse Au-NPs were prepared by reacting 4′-aminobenzo-18-crown-6 with carbon disulfide to generate the dithiocarbamate ligand which was then added to the Au-NPs to form a supramolecular assembly on their surface. The Au-NPs modified in this way undergo aggregation in the presence of Pb(II) ions, and this causes the color to change from red to blue. The Pb(II)-induced aggregation can be monitored by using UV-visible spectrometry and even with the bare eye. The absorbance ratio (A 650nm /A 520nm ) is linearly related to the concentration of Pb(II) in the 0.1 to 75 μM range (with a correlation coefficient of 0.9957), and the detection limit is 50 nM which is lower than the allowable level (75 nM) as defined by the US EPA. The method was successfully applied to the determination of Pb(II) in spiked water samples. (author)

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Indian Academy of Sciences (India)

Investigation on silver complexes of novel 1,2,3-triazole linked crown ethers by ... Bent Shaped 1,3,4-Oxadiazole/Thiadiazole heterocyclic rings containing liquid ... Design, synthesis and characterization of 1 H-pyridin-4-yl-3, 5- disubstituted ...

Exogenous ether lipids predominantly target mitochondria.

Directory of Open Access Journals (Sweden)

Lars Kuerschner

Full Text Available Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria in ether lipid metabolism and intracellular ether lipid trafficking.

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...

Ether formulations of relativity

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Contemporary ether theories are surveyed and criticised, especially those formally identical to orthodox Relativity. The historical development of Relativity, Special and General, in terms of an ether, is briefly indicated. Classical interpretations of Generalized Relativity using ether are compared to Euclidean formulations using a background space. The history of a sub-group of theories, formulating a 'new' Relativity involving modified transforms, is outlined. According to the theory with which they agree, recent supposed detections of drift are classified and criticised. Cosmological evidence suggesting an ether is mentioned. Only ether theories formally identical to Relativity have been published in depth. They stand criticised as being contrary to the positivist spirit. The history of mechanical analogues is traced, from Hartley's representing gravitating matter as spherical standing waves, to recent suggestions that vortex-sponge might model electromagnetic, quantum, uncertainty and faster-than-light phenomena. Contemporary theories are particular physical theories, themselves 'second interpretations' of a primary mathematical model. Mechanical analogues are auxiliary, not necessary, to other theory, disclosing relationships between classical and non-classical descriptions of assemblies charging state. The ether-relativity polemic, part of a broader dispute about relativity, is founded on mistaken conceptions of the roles of mathematical and physical models, mechanical analogues; and a distored view of history, which indicates that ether theories have become relativistic. (author)

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

Increased Yield of Biotransformation of Androsta-1, 4-Dien-3, 17-Dione from Β-Sitosterol by Using Sulfobutyl Ether-Β-Cyclodextrin Complexation Technique

Directory of Open Access Journals (Sweden)

Wang Jingwen

2016-01-01

Full Text Available Substrate solubility in steroid biotransformation is critical for enhancing the biotransformation of hydrophobic compounds. In this study, the sulfobutyl ether-β-cyclodextrin (SBE-β-CD complexation technique was used for the biotransformation of β-sitosterol to androsta-1, 4-diene-3, 17-dione with Mycobacterium ATCC25795. The production yield was increased by 26.72%, and the biotransformation course was shortened by 24h using β-sitosterol/SBE-β-CD inclusion complexes as substrates (1.0 g/L. Fourier transform infrared spectroscopy and differential scanning calorimetry indicated that an inclusion complex was formed between SBE-β-CD and β-sitosterol. The complex significantly increased the solubility of β-sitosterol and improved the biotransformation efficiency of the substrate.

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.

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.

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...

[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.

Designing molecular complexes using free-energy derivatives from liquid-state integral equation theory

International Nuclear Information System (INIS)

Mrugalla, Florian; Kast, Stefan M

2016-01-01

Complex formation between molecules in solution is the key process by which molecular interactions are translated into functional systems. These processes are governed by the binding or free energy of association which depends on both direct molecular interactions and the solvation contribution. A design goal frequently addressed in pharmaceutical sciences is the optimization of chemical properties of the complex partners in the sense of minimizing their binding free energy with respect to a change in chemical structure. Here, we demonstrate that liquid-state theory in the form of the solute–solute equation of the reference interaction site model provides all necessary information for such a task with high efficiency. In particular, computing derivatives of the potential of mean force (PMF), which defines the free-energy surface of complex formation, with respect to potential parameters can be viewed as a means to define a direction in chemical space toward better binders. We illustrate the methodology in the benchmark case of alkali ion binding to the crown ether 18-crown-6 in aqueous solution. In order to examine the validity of the underlying solute–solute theory, we first compare PMFs computed by different approaches, including explicit free-energy molecular dynamics simulations as a reference. Predictions of an optimally binding ion radius based on free-energy derivatives are then shown to yield consistent results for different ion parameter sets and to compare well with earlier, orders-of-magnitude more costly explicit simulation results. This proof-of-principle study, therefore, demonstrates the potential of liquid-state theory for molecular design problems. (paper)

Co-extraction of Strontium and Cesium by Dicyclohexano-18 Crown-6/25, 27-Bis(2- Propyloxy)Calix[4]-26, 28-Crown-6{sup ..}Cn-Octanol

Energy Technology Data Exchange (ETDEWEB)

Ye, W.L.; Wang, J.CH.; He, Q.G. [Institute of Nuclear and New Energy Technology, Tsinghua University, P.O. Box 1021, Beijing 102201 (China)

2009-06-15

The partitioning of {sup 90}Sr and {sup 137}Cs from high-level liquid waste(HLLW) is one of the important problems for the high-level waste volume reduction and the management of HLLW. The crown ether and calix-crown have the good extracting ability and selectivity to strontium and cesium respectively. Dicyclohexano-18Crown-6 (DCH18C-6) and 25, 27-Bis(2-propyloxy) Calix[4] -26, 28- Crown-6(IPR-C[4]C-6) were selected as extractants and n-octanol was selected as the common diluent to separate strontium and cesium from high-level liquid waste respectively in INET's Tsinghua University, China. But DCH18C- 6 and IPR-C[4]C-6 were used respectively in their processes to separate strontium and cesium. The strontium and cesium processes could be simplified if DCH18C-6 and IPR-C[4]C-6 processes are combined into one process to separate strontium and cesium together. In this paper, the co-extraction performance of strontium and cesium from nitric acid medium was studied by DCH18C-6 /IPR-C[4]C-6 and n-octanol as an diluent. Effects of extractant concentration, nitric concentration and temperature etc. on the extraction performance of strontium and cesium were studied. The results show that DCH18C-6 and IRP-C[4]C-6 in n-octanol has no synergistic extraction ability each other to strontium and cesium. Strontium and cesium were extracted independently by above two extractants. 0.1 mol/L DCH18C-6 and 0.025 mol/L /IPR-C[4]C-6 as extractants and n-octanol as a diluent were selected to separate strontium and cesium from HLLW. The cascade test in which was 10 stages for extraction, 2 stages for scrubbing and 8 stages for stripping was carried out on the miniature centrifugal contactor set. The results are the following: the removing ratios for strontium and cesium in the simulated HLLW were 98.93% and 99.93%, respectively; the stripping ratios of them were 99.80% and 99.79%, respectively. So the mixing extractants could be used to co-extract strontium and cesium from HLLW and

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.

Ether the nothing that connects everything

CERN Document Server

Milutis, Joe

2006-01-01

In Ether, the histories of the unseen merge with discussions of the technology of electromagnetism. Navigating more than three hundred years of the ether''s cultural and artistic history, Joe Milutis reveals its continuous reinvention and tangible impact without ever losing sight of its ephemeral, elusive nature. The true meaning of ether, Milutis suggests, may be that it can never be fully grasped.

Usage of the word 'ether'

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Confusion has been caused by scientists using the one word 'ether' to classify models differing from each other in important respects. Major roles assigned to the word are examined, and the nature of modern ether theories surveyed. The part played by the several meanings attached to the word, in the ether concept, is outlined. (author)

Chromoionophoric Recognition of Alkylamines by Nitro Derivative

International Nuclear Information System (INIS)

Kim, Ju Hee; Hwang, Ah Ran; Choe, Jong In; Chang, Suk Kyu

2004-01-01

The molecular design of efficient and selective chromogenic and fluorogenic ionophore systems for the sensing of chemically and biologically important ionic guests has attracted much attention in the past decade. Many of the compounds are based on the well-known molecular framework of crown ethers, calixarenes, and other EDTA type efficient chelating compounds. Among them the calix[4]arenes are particularly attractive for their selective ionophoric properties toward many of interesting organic ammonium guests. Particularly, the calix[4]arene-crown ethers are known to have unique binding properties toward some of alkali, alkaline earth metal ions, and biogenic amines. Many of the chromogenic sensing materials are developed by conjugating molecular framework of calix[4]- arene-crown ethers with suitable signaling functions of azophenols, thiazoles, and indophenols. Quite unexpectedly, however, the ionophoric properties of simple nitro derivative of calix[4]arene-crown ethers were not reported, except for the closely related structure having ester-ether functions in crown moiety, in spite of their synthetically easy availability and expectedly efficient ionophoric properties toward organic amine guests. In this paper, we report the ionophoric properties of dinitro derivative of calix[4]arene-crown-5 ether 1 toward representative alkylammonium ions aiming for the development of efficient and selective chromogenic sensing material for the biologically important organic amine guests. The Ba 2+ -selective chromogenic behavior of 1 over the representative alkali and alkaline earth metal ions has been reported earlier.

The failure of poly (ether ether ketone) in high speed contacts

Science.gov (United States)

Briscoe, B. J.; Stuart, B. H.; Sebastian, S.; Tweedale, P. J.

1993-04-01

The paper describes an experimental study, with an associated analysis incorporating supplementary data, of the anti-boundary lubricating action of an alkane-aliphatic carboxylic acid lubricant system in a poly (ether ether ketone)-mild steel contact. The experiments involve progressively increasing the load in a contact formed between a polymer plate and a rotating steel shaft and estimating the frictional work dissipated. Scuffing is identified when a rapid increase in frictional work is noted at a characteristic normal load. It is shown that the additive induces premature scuffing. Subsidiary data is provided using Raman spectroscopy and hardness probes, and confirms that certain additives such as decanoic acid and dodecylamine will induce surface plasticization in poly (ether ether ketone). The trends in the frictional data have been interpreted using the adhesive model of friction in conjunction with temperature-dependent interfacial theology and bulk mechanical property data. It is proposed that the scuffing process is induced prematurely as a consequence of excessive additive-induced subsurface plasticization. Restricted surface plasticization in this system provides an enhanced self-lubricating capacity.

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...

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 ...

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.

Basic randomness of nature and ether-drift experiments

International Nuclear Information System (INIS)

Consoli, M.; Pluchino, A.; Rapisarda, A.

2011-01-01

Highlights: ► We re-consider the idea of a basic randomness of nature. ► We adopt Stochastic Electro Dynamics as a heuristic model. ► We represent the vacuum as a form of turbulent ether. ► This picture can be tested with forthcoming ether-drift experiments. - Abstract: We re-consider the idea that quantum fluctuations might reflect the existence of an ‘objective randomness’, i.e. a basic property of the vacuum state which is independent of any experimental accuracy of the observations or limited knowledge of initial conditions. Besides being responsible for the observed quantum behavior, this might introduce a weak, residual form of ‘noise’ which is intrinsic to natural phenomena and could be important for the emergence of complexity at higher physical levels. By adopting Stochastic Electro Dynamics as a heuristic model, we are driven to a picture of the vacuum as a form of highly turbulent ether, which is deep-rooted into the basic foundational aspects of both quantum physics and relativity, and to search for experimental tests of this scenario. An analysis of the most precise ether-drift experiments, operating both at room temperature and in the cryogenic regime, shows that, at present, there is some ambiguity in the interpretation of the data. In fact the average amplitude of the signal has precisely the magnitude expected, in a ‘Lorentzian’ form of relativity, from an underlying stochastic ether and, as such, might not be a spurious instrumental effect. This puzzle, however, should be solved in a next future with the use of new cryogenically cooled optical resonators whose stability should improve by about two orders of magnitude. In these new experimental conditions, the persistence of the present amplitude would represent a clean evidence for the type of random vacuum we are envisaging.

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.

Study of the sorption of nuclear fuel fission products using non-ion exchange polymeric and inorganic materials

International Nuclear Information System (INIS)

Manorik, P.

1997-01-01

New tetrazamacrocycle and crown-ether poly-styrene and divinylbenzenepolystyrene derivatives (P-TAM and P-CE respectively) have been synthesized and studied as chemisorbents for Cs, Sr (P-CE) and Ru, Co (P-TAM) radioisotopes. It has been found that the tetraazamacro cycle modifier concentration in such material is about 5 x 10 -4 M/g material. Model solutions, containing Ru and other platinoid salts, and also Co salts, were used in experiments at concentrations of 5 x 10 -3 - 5 x 10 -6 M/L. It was shown that P-TAM quantitatively removes Ru and other platinoids from the water solution at pH = 0-1 during 1-2 days and practically all modifying groups participate in the sorption process. It was established that in alkaline solutions this sorbent also adsorbs Co, Cr and other 3d-metal ions. P-TAM also demonstrates a very high platinoid sorption selectivity (close to 100%) from solutions containing, for example, platinoids in the presence of a large excess of 3d-metal ions. 137 Cs sorption by some types of P-CE and IN-CE from Ringer-Locka model waste solution was also studied and it was found that K d (Bq/g) strongly depends not only on the crown-ether ring size but also on the form in which crown-ethers exist on the surface, for example when the modifier was in the form of the complex such as P-CE-L(L=K 3 Fe(CN) 6 or L=K 4 Fe(CN) 6 ) there was an increase in K' d value (Bq/mole of CE). The results of a study of 85 Sr removal by P-CE and IN-CE show that the chemisorption capacity strongly depends not only on the ''hole'' size of crown-ethers but also on the nature of encapsulated complexes, including ferrocyanides of different types. 32 refs, 5 figs, 5 tabs

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.

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.

Novel Fission-Product Separation Based on Room-Temperature Ionic Liquids

International Nuclear Information System (INIS)

Rogers, Robin D.

2004-01-01

This project has demonstrated that Sr2+ and Cs+ can be selectively extracted from aqueous solutions into ionic liquids using crown ethers and that unprecedented large distribution coefficients can be achieved for these fission products. The volume of secondary wastes can be significantly minimized with this new separation technology. Through the current EMSP funding, the solvent extraction technology based on ionic liquids has been shown to be viable and can potentially provide the most efficient separation of problematic fission products from high level wastes. The key results from the current funding period are the development of highly selective extraction process for cesium ions based on crown ethers and calixarenes, optimization of selectivities of extractants via systematic change of ionic liquids, and investigation of task-specific ionic liquids incorporating both complexant and solvent characteristics

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.

Mechanisms and kinetics of electrodeposition of alkali metals on solid and liquid mercury electrodes

Energy Technology Data Exchange (ETDEWEB)

Lu, Wenzhe.

1993-01-01

Electroreduction of alkali metal ions at mercury is an important area in electrochemistry related to the battery industry. In this work, four major topics were considered: alkali metal/mercury interactions; electrosorption of alkali metal ions on solid mercury; electroreduction of alkali metal/crown ether complexes; and ammonium amalgam formation. The formation of alkali metal-mercury intermetallic compounds was studied on liquid and frozen thin layer mercury electrodes. The stoichiometry of the compounds produced under these conditions was determined using cyclic voltammetry. As expected, formation of a new phase was preceded by nucleation phenomena, which were particularly easy to monitor at solid Hg electrodes. The nucleation kinetics were studied using the chronoamperometric method. At very low temperatures, when the mobility of mercury atoms was restricted, the electrosorption of alkali metal ions on solid mercury electrodes was noted. Subsequent study allowed determination of the electrosorption parameters. The free energy of electrosorption is discussed in terms of interactions between alkali metals and mercury. The effect of crown ethers on the kinetics of alkali metal ion reduction was studied at both standard size and ultramicro-mercury electrodes in nonaqueous solutions using ultrafast cyclic voltammetry and ac voltammetry. The usefulness of ultrafast cyclic voltammetry with ultramicroelectrodes in measurements of the kinetics of amalgam formation was verified in a brief study of cadmium ion reduction. The mechanism of the complex reduction at mercury was analyzed based on the free energy changes before and after the activation state. In addition, the stoichiometry and formation constants of the crown ether/alkali metal complexes were determined using cyclic voltammetry. The mechanism of electroreduction of ammonium ions at mercury electrodes in non-aqueous media was analyzed.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 119; Issue 2. Comparative photophysical behaviour of naphthalene-linked crown ethers and aza crown ethers of varying cavity dimensions. Subhodip Samanta Pinki Saha Sardar Shyam Sundar Maity Anirban Pal Maitrayee Basu Roy Sanjib Ghosh. Volume 119 Issue ...

A green strategy for lithium isotopes separation by using mesoporous silica materials doped with ionic liquids and benzo-15-crown-5

International Nuclear Information System (INIS)

Wen Zhou; Xiao-Li Sun; Lin Gu; Fei-Fei Bao; Xin-Xin Xu; Chun-Yan Pang; Zaijun Li; Zhi-Guo Gu; Jiangnan University, Wuxi

2014-01-01

Three new mesoporous silica materials IL15SGs (HF15SG, TF15SG and DF15SG) doped with benzo-15-crown-5 and imidazolium based ionic liquids (C 8 mim + PF 6 - , C 8 mim + BF 4 - or C 8 mim + NTf 2 - ) have been prepared by a simple approach to separating lithium isotopes. The formed mesoporous structures of silica gels have been confirmed by transmission electron microscopy image and N 2 gas adsorption-desorption isotherm. Imidazolium ionic liquids acted as templates to prepare mesoporous materials, additives to stabilize extractant within silica gel, and synergetic agents to separate the lithium isotopes. Factors such as lithium salt concentration, initial pH, counter anion of lithium salt, extraction time, and temperature on the lithium isotopes separation were examined. Under optimized conditions, the extraction efficiency of HF15SG, TF15SG and DF15SG were found to be 11.43, 10.59 and 13.07 %, respectively. The heavier isotope 7 Li was concentrated in the solution phase while the lighter isotope 6 Li was enriched in the gel phase. The solid-liquid extraction maximum single-stage isotopes separation factor of 6 Li- 7 Li in the solid-liquid extraction was up to 1.046 ± 0.002. X-ray crystal structure analysis indicated that the lithium salt was extracted into the solid phase with crown ether forming [(Li 0.5 ) 2 (B 15 ) 2 (H 2 O)] + complexes. IL15SGs were also easily regenerated by stripping with 20 mmol L -1 HCl and reused in the consecutive removal of lithium ion in five cycles. (author)

Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

Directory of Open Access Journals (Sweden)

Zilu Yao

2017-11-01

Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

Critical properties of some aliphatic symmetrical ethers

International Nuclear Information System (INIS)

Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

2014-01-01

Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

Radiation-induced cationic curing of vinyl ethers

International Nuclear Information System (INIS)

Lapin, S.C.

1992-01-01

Recently there has been an increasing interest in nonacrylate radiation-curable coatings. Vinyl ethers are particularly reactive under cationic polymerization reaction conditions. The high efficiency of the photoacid initiators combined with the high reactivity of vinyl ether monomers makes this a potentially very useful system. This chapter discusses the preparation of vinyl ethers, introduces vinyl ether-functional monomers and oligomers, describes radiation-induced cationic polymerization of vinyl ethers, and discusses various coating systems. Throughout the chapter, an emphasis is placed on radiation-curable coating applications. 64 refs., 5 figs., 11 tabs

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

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 ...

Poly (ether ether ketone) membranes for fuel cells

International Nuclear Information System (INIS)

Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D.; Hui, Wang S.; Oliveira, Vivianna S. de

2015-01-01

Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

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

Copper Promoted Synthesis of Diaryl Ethers

OpenAIRE

Ghosh, Rajshekhar; Samuelson, Ashoka G

2004-01-01

An efficient protocol using copper based reagents for the coupling of aryl halides with phenols to generate diaryl ethers is described. Acopper( I) complex, [ Cu( CH3CN) (4)] ClO4, or the readily available copper( II) source, CuCO3 . Cu( OH) (2) . H2O ( in combination with potassium phosphate), can be used. Aryl halides and phenols with different steric and electronic demands have been used to assess the efficiency of the procedure. The latter source of copper gives better yields under all co...

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

Energy Technology Data Exchange (ETDEWEB)

Rustenholtz Farawila, A

2005-06-15

Supercritical fluid carbon dioxide (SF-CO{sub 2}) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO{sub 2}. A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO{sub 2} phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO{sub 2}. For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO{sub 2}. These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO{sub 2} for the extraction of uranium from ash. (author)

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

International Nuclear Information System (INIS)

Rustenholtz Farawila, A.

2005-06-01

Supercritical fluid carbon dioxide (SF-CO 2 ) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO 2 . A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO 2 phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO 2 . For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO 2 . These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO 2 for the extraction of uranium from ash. (author)

Preparation of Sr adsorptive fiber by impregnating with crown ether derivative for 90Sr measurement

International Nuclear Information System (INIS)

Horita, Takuma; Asai, Shiho; Hanzawa, Yukiko; Kitatsuji, Yoshihiro; Konda, Miki; Saito, Kyoichi; Fujiwara, Kunio; Sugo, Takanobu

2017-01-01

A Sr adsorption fiber was prepared for rapid analysis of 90 Sr content in the fiber using radiation-induced emulsion graft polymerization and subsequent chemical modification. A polyethylene fiber with a diameter of 13 μm was first immersed in a methanol solution of an epoxy-group-containing vinyl monomer, glycidyl methacrylate (GMA), and polyoxyethylene sorbitol ester (Tween20) as a surfactant for the graft-polymerization of GMA. Octadecylamine was then bound to a polymer chain extending from the fiber surface, providing hydrophobicity to the polymer chain. Dicyclohexano-18-crown-6 (DCH18C6) was finally impregnated onto the polymer chain via a hydrophobic interaction between the octadecyl moiety of the polymer chain and the cyclohexyl moiety of DCH18C6. The fiber surface structure, characterized by DCH18C6 molecules loosely entangled with polymer chains, allowed for the rapid adsorption of Sr ions at an adsorption rate of approximately 100-times higher than that of a commercially available Sr-selective resin (Sr Resin ® ). (author)

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.

Hydrogen storage by functionalised Poly(ether ether ketone)

Energy Technology Data Exchange (ETDEWEB)

Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

2010-07-01

In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

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.

On solvent extraction of metals by macrocyclic polyethers

International Nuclear Information System (INIS)

Ionov, V.P.

1984-01-01

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

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.

Synthesis and Characterization of Sulfonated Graphene Oxide Reinforced Sulfonated Poly (Ether Ether Ketone (SPEEK Composites for Proton Exchange Membrane Materials

Directory of Open Access Journals (Sweden)

Ning Cao

2018-03-01

Full Text Available As a clean energy utilization device, full cell is gaining more and more attention. Proton exchange membrane (PEM is a key component of the full cell. The commercial-sulfonated, tetrafluoroethylene-based fluoropolymer-copolymer (Nafion membrane exhibits excellent proton conductivity under a fully humidified environment. However, it also has some disadvantages in practice, such as high fuel permeability, a complex synthesis process, and high cost. To overcome these disadvantages, a low-cost and novel membrane was developed. The sulfonated poly (ether ether ketone (SPEEK was selected as the base material of the proton exchange membrane. Sulfonated graphene (SG was cross-linked with SPEEK through the elimination reaction of hydrogen bonds. It was found that the sulfonic acid groups and hydrophilic oxygen groups increased obviously in the resultant membrane. Compared with the pure SPEEK membrane, the SG-reinforced membrane exhibited better proton conductivity and methanol permeability prevention. The results indicate that the SG/SPEEK could be applied as a new proton exchange membrane in fuel cells.

Biaxial deformation behaviour of poly-ether-ether-ketone

Science.gov (United States)

Turner, Josh; Menary, Gary; Martin, Peter

2018-05-01

The biaxial tensile properties of thin poly-ether-ether-ketone (PEEK) films are presented. Investigation into the biaxial mechanical behaviour of PEEK films will provide a preliminary insight into the anticipated stress/strain response, and potential suitability, to the possible fabrication of thin walled parts through stretch blow moulding and thermoforming processes - with the multi-axial state of strain imposed onto the heated thermoplastic sheet representative of the expected strain history experienced during these material forming processes. Following identification of the prospective forming temperature window, the biaxial mechanical behaviour of the material is characterized under differing modes of deformation, at a nominal strain rate of 1 s-1. The temperature dependence is outlined within - with an appreciable increase in flow behaviour correlated with specimen temperature exceeding its glass transition temperature (Tg).

Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

Science.gov (United States)

Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

2011-07-14

Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

Preparation and Characterization of Sulfonated Poly (ether ether ...

African Journals Online (AJOL)

NJD

2007-08-10

Aug 10, 2007 ... Preparation and Characterization of Sulfonated Poly (ether ... Currently perfluori- ... with phosphoric acid solution according to the method described earlier.11,12 ... where A is the membrane area available for diffusion; CA is.

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

Science.gov (United States)

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

2017-11-21

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

Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

2013-10-01

Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

International Nuclear Information System (INIS)

Chiu, K.-F.; Su, S.-H.

2013-01-01

Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

Gold( i )-catalysed dehydrative formation of ethers from benzylic alcohols and phenols

KAUST Repository

Veenboer, Richard M. P.

2015-01-01

© The Royal Society of Chemistry 2015. We report the cross-dehydrative reaction of two alcohols to form unsymmetrical ethers using NHC-gold(i) complexes (NHC = N-heterocyclic carbene). Our progress in developing this reaction into a straightforward procedure is discussed in detail. The optimised methodology proceeds under mild reaction conditions and produces water as the sole by-product. The synthetic utility of this environmentally benign methodology is exemplified by the formation of a range of new ethers from readily available phenols bearing electron withdrawing substituents and secondary benzylic alcohols with various substituents. Finally, we present experimental results to account for the chemoselectivity obtained in these reactions.

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...

Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

NARCIS (Netherlands)

Koziara, B.T.; Nijmeijer, K.; Benes, N.E.

2015-01-01

The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (≤5 wt%) and not too low spin speeds

Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

NARCIS (Netherlands)

Koziara, Beata; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

2015-01-01

The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (B5 wt%) and not too low spin speeds

Implementation and Validation of EtherCAT Support in Integrated Development Environment for Synchronized Motion Control Application

Energy Technology Data Exchange (ETDEWEB)

Lee, Jongbo; Kim, Chaerin; Kim, Ikhwan; Kim, Youngdong; Kim, Taehyoun [Univ. of Seoul, Seoul (Korea, Republic of)

2014-02-15

Recently, software-based programmable logic controller (PLC) systems, which are implemented in standard PLC languages on general hardware, are gaining popularity because they overcome the limitations of classical hardware PLC systems. Another noticeable trend is that the use of integrated development environment (IDE) is becoming important. IDEs can help developers to easily manage the growing complexity of modern control systems. Furthermore, industrial Ethernet, e. g. EtherCAT, is becoming widely accepted as a replacement for conventional fieldbuses in the distributed control domain because it offers favorable features such as short transmission delay, high bandwidth, and low cost. In this paper, we implemented the extension of open source IDE, called Beremiz, for developing EtherCAT-based real-time, synchronized motion control applications. We validated the EtherCAT system management features and the real-time responsiveness of the control function by using commercial EtherCAT drives and evaluation boards.

Inert and stable erbium(III)-cored complexes based on metalloporphyrins bearing aryl-ether dendron for optical amplification: synthesis and emission enhancement

International Nuclear Information System (INIS)

Oh, Jae Buem; Kim, Yong Hee; Nah, Min Kook; Kim, Hwan Kyu

2005-01-01

We have developed novel inert and stable erbium (Er)(III)-cored complexes based on metalloporphyrins for optical amplification. The functionalized metalloporphyrin ligands have been designed and synthesized to provide enough coordination sites for the formation of inert and stable 9-coordinated Er(III)-cored complexes. Er 3+ ions were encapsulated by the metalloporphyrin ligands, such as Zn(II)- and Pt(II)-porphyrins. The near-infrared (IR) emission intensity of Er 3+ ion is much stronger in the Er(III)-cored complex based on Pt(II)-porphyrin than Er(III)-cored complex based on Zn(II)-porphyrin. Furthermore, we have incorporated a G2-aryl-ether functionalized dendron into the Er(III)-cored complex, yielding an Er(III)-cored dendrimer complex bearing the Pt(II)-porphyrin. The Er(III)-cored dendrimer complex shows the stronger near-IR emission intensity than the corresponding complex based on Pt(II)-porphyrin by seven times in solid state. The lifetimes of the emission band of Pt(II)-porphyrin ligands in the visible region were found to be 30 and 40 μs for the Er(III)-cored complex and the Er(III)-cored dendrimer complex based on Pt(II)-porphyrin in deoxygenated THF solution samples, respectively. Also, in both cases, the sensitized luminescence intensity is increased in deoxygenated solution. Therefore, it indicates that the energy transfer from the metalloporphyrins to Er 3+ ions takes places through the triplet state. In this paper, the synthesis and photophysical properties of novel Er(III)-cored complexes based on metalloporphyrins and Er(III)-cored dendrimer complex based on metalloporphyrin will be discussed

Transport of strontium and some 1. and 2. group's cations through hollow fiber supported liquid membranes using crowns

International Nuclear Information System (INIS)

Mackova, J.

1996-01-01

Models which describe the permeation of strontium cation through liquid membranes are shown in this paper. Partition coefficients have been determined radiometrically, using Sr-85 tracer. The results were treated according to the theory developed by Danesi using simple equation. The permeation of Sr 2+ using 18-crown-6 crown ether (18C6) and picric acid in bulk liquid toluene membrane systems with and without surface/active substances (SPAN 80, ECA 4360) has been studied. The transport of Sr 2+ using 18-C-6 ether as a carrier and picrate as a co-counter ion through hollow fiber supported dichlorobenzene liquid membrane has been studied too. A polypropylene hollow fiber ACCUREL PP type S6/ENKA and a permeation device with a single hollow fiber module with on-line radiometric detection of strontium using Sr-85 tracer, was used. This type of permeation system has shown reproducible results, fast and effective permeation. Results prove the possible mechanism of strontium cation transport though liquid membrane. Another subject of study was the transport of metal ions (Ca 2+ , Sr 2+ , Ba 2+ , Na + , K + , Cs + ) using (18C6) as a carrier and picrate as co/counter ion through hollow fiber supported dichlorobenzene liquid membrane using capillary isotachophoresis (ITP) measurement of the cations concentration. The experimental results obtained using ITP method for Sr 2+ concentration determination are in good agreement with those obtained by on-line radiometric detection using Sr-85 tracer, under the same conditions (feed, membrane, strip, hollow fiber and the same pertraction device). The ITP method could be successfully used for analyses of samples containing a mixture of all separated cations. The results of this study indicate that the polypropylene hollow fiber supported dichlorobenzene membrane is suitable for studied metal cation transport using 18C6 as a carrier and a picrate as co-counter ion. This combination enables fast and effective cation separation. The

Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

Energy Technology Data Exchange (ETDEWEB)

Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

2014-02-15

Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

Thermal stability of sulfonated Poly(Ether Ether Ketone) films : on the role of Protodesulfonation

NARCIS (Netherlands)

Koziara, B.T.; Kappert, E.J.; Ogieglo, W.; Nijmeijer, Kitty; Hempenius, M.A.; Benes, N.E.

Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material,

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

Leaching characteristics of polybrominated diphenyl ethers (PBDEs) from flame-retardant plastics.

Science.gov (United States)

Kim, Yong-Jin; Osako, Masahiro; Sakai, Shin-ichi

2006-10-01

To investigate the effect of leachant on the leachability of polybrominated diphenyl ethers (PBDEs), we determined the leaching concentrations of PBDEs from flame-retardant plastic samples (TV housings and raw materials before molding processing) that are regarded as a source of PBDEs in landfill sites. The leachants used were distilled water, 20% methanol solution, and dissolved humic solution (DHS) of 1000 mg/l based on organic carbon. The leaching test conditions were a liquid-to-solid ratio of 100:1, and a contact period of five days, with twice-daily agitation in a temperature-controlled room of 30 degrees C without pH or ionic strength control. The leaching concentrations of PBDEs increased with increased content, and were found to be remarkably enhanced when methanol and DHS were used instead of distilled water. The enhancement of leachability in the presence of the latter was attributed to the cosolvency effect, and complex formations between the PBDEs and dissolved humic matter (DHM). PBDE concentrations in the leachate obtained from the leaching test and an actual landfill site revealed a significant presence of congeners below heptabromodiphenyl ethers (H7BDEs), detected in the leachate of the actual landfill, while significant amounts of nonabromodiphenyl ethers (N9BDEs) and decabromodiphenyl ether (D10BDE) were detected in the leachate of the leaching test.

Photosynthesis involvement in the mechanism of action of diphenyl ether herbicides.

Science.gov (United States)

Ensminger, M P; Hess, F D

1985-05-01

Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1'-dimethyl-4,4'-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity.

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.

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...

Terminal parent phosphanide and phosphinidene complexes of zirconium(IV)

Energy Technology Data Exchange (ETDEWEB)

Stafford, Hannah; Rookes, Thomas M.; Wildman, Elizabeth P.; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Balazs, Gabor; Scheer, Manfred [Institute of Inorganic Chemistry, University of Regensburg (Germany)

2017-06-19

The reaction of [Zr(Tren{sup DMBS})(Cl)] [Zr1; Tren{sup DMBS}=N(CH{sub 2}CH{sub 2}NSiMe{sub 2}Bu{sup t}){sub 3}] with NaPH{sub 2} gave the terminal parent phosphanide complex [Zr(Tren{sup DMBS})(PH{sub 2})] [Zr2; Zr-P=2.690(2) Aa]. Treatment of Zr2 with one equivalent of KCH{sub 2}C{sub 6}H{sub 5} and two equivalents of benzo-15-crown-5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition-metal terminal parent phosphinidene complex [Zr(Tren{sup DMBS})(PH)][K(B15C5){sub 2}] [Zr3; Zr=P=2.472(2) Aa]. DFT calculations reveal a polarized-covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic-type Zr..HP interaction [ angle {sub ZrPH}=66.7 ] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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. 

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.

On new physical reality (on ψ-ether)

International Nuclear Information System (INIS)

Isaev, P.S.

2002-01-01

It is shown that there exists a new physical reality - the ψ-ether. All the achievements of quantum mechanics and quantum field theory are due to the fact that both the theories include the influence of ψ-ether on the physical processes occurring in the Universe. Physics of the XX century was first of all the physics of ψ-ether

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.

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...

Isolation by crystallization of translational isomers of a bistable donor-acceptor [2]catenane

Science.gov (United States)

Wang, Cheng; Olson, Mark A.; Fang, Lei; Benítez, Diego; Tkatchouk, Ekaterina; Basu, Subhadeep; Basuray, Ashish N.; Zhang, Deqing; Zhu, Daoben; Goddard, William A.; Stoddart, J. Fraser

2010-01-01

The template-directed synthesis of a bistable donor-acceptor [2]catenane wherein both translational isomers—one in which a tetrathiafulvalene unit in a mechanically interlocked crown ether occupies the cavity of a cyclobis(paraquat-p-phenylene) ring and the other in which a 1,5-dioxynaphthalene unit in the crown ether resides inside the cavity of the tetracationic cyclophane—exist in equilibrium in solution, has led to the isolation and separation by hand picking of single crystals colored red and green, respectively. These two crystalline co-conformations have been characterized separately at both the molecular and supramolecular levels, and also by dynamic NMR spectroscopy in solution where there is compelling evidence that the mechanically interlocked molecules are present as a complex mixture of translational, configurational, and conformational isomers wherein the isomerization is best described as being a highly dynamic and adaptable phenomenon. PMID:20663950

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.

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

International Nuclear Information System (INIS)

Gibelli, Edison Bessa

2010-01-01

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

Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

Energy Technology Data Exchange (ETDEWEB)

Fayolle-Guichard, F

2005-04-01

Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

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...

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.

Sulfonated poly(ether ether ketone) membranes for electric double layer capacitors

International Nuclear Information System (INIS)

Kim, Wan Ju; Kim, Dong-Won

2008-01-01

Sulfonated poly(ether ether ketone) (S-PEEK) with different degree of sulfonation (DS) has been prepared and evaluated as a proton conducting membrane for electric double layer capacitor (EDLC). The polymer electrolytes prepared with S-PEEK membrane exhibited ionic conductivities about 1.2 x 10 -3 -4.5 x 10 -3 S cm -1 at room temperature, which depended on both soaking solvent and degree of sulfonation. The quasi-solid-state EDLCs consisted of activated carbon electrodes and S-PEEK membrane were assembled, and their electrochemical characteristics were studied by cyclic voltammetry and charge-discharge cycle tests. The effect of DS on the electrochemical performances of EDLCs has been investigated

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...

Photosynthesis Involvement in the Mechanism of Action of Diphenyl Ether Herbicides 1

Science.gov (United States)

Ensminger, Michael P.; Hess, F. Dan

1985-01-01

Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1′-dimethyl-4,4′-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity. PMID:16664206

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.

Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

Science.gov (United States)

Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

2014-06-01

Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

[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

Chemoselective Deprotection of Triethylsilyl Ethers

Science.gov (United States)

Chandra, Tilak; Broderick, William E.; Broderick, Joan B.

2009-01-01

An efficient and selective method was developed for the deprotection of triethylsilyl (TES) ethers using formic acid in methanol (5–10%) or in methylene chloride 2–5%) with excellent yields. TES ethers are selectively deprotected to the corresponding alcohols in high yields using formic acid in methanol under mild reaction conditions. Other hydroxyl protecting groups like t-butyldimethylsilyl (TBDMS) remain unaffected. PMID:20183570

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.)

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')

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Science.gov (United States)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Energy Technology Data Exchange (ETDEWEB)

Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

2018-03-06

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

Science.gov (United States)

Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

2017-09-01

Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

Laser spectroscopic and theoretical studies of the structures and encapsulation motifs of functional molecules

Energy Technology Data Exchange (ETDEWEB)

Ebata, Takayuki; Kusaka, Ryoji [Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, 739-8526 (Japan); Xantheas, Sotiris S. [Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (United States)

2015-01-22

Extensive laser spectroscopic and theoretical studies have been recently carried out with the aim to reveal the structure and dynamics of encapsulation complexes in the gas phase. The characteristics of the encapsulation complexes are governed by the fact that (i) most of the host molecules are flexible and (ii) the complexes form high dimensional structures by using weak non-covalent interactions. These characteristics result in the possibility of the coexistence of many conformers in close energetic proximity. The combination of supersonic jet/laser spectroscopy and high level quantum chemical calculations is essential in tackling these challenging problems. In this report we describe our recent studies on the structures and dynamics of the encapsulation complexes formed by calix[4]arene (C4A), dibenzo-18-crown-6-ether (DB18C6), and benzo-18-crown-6-ether (B18C6) 'hosts' interacting with N{sub 2}, acetylene, water, and ammonia 'guest' molecules. The gaseous host-guest complexes are generated under jet-cooled conditions. We apply various laser spectroscopic methods to obtain the conformer- and isomer-specified electronic and IR spectra. The experimental results are complemented with quantum chemical calculations ranging from density functional theory to high level first principles calculations at the MP2 and CCSD(T) levels of theory. We discuss the possible conformations of the bare host molecules, the structural changes they undergo upon complexation, and the key interactions that are responsible in stabilizing the specific complexes.

Microwave sintering of poly-ether-ether-ketone (PEEK) based coatings deposited on metallic substrate

International Nuclear Information System (INIS)

Zhang, G.; Leparoux, S.; Liao, H.; Coddet, C.

2006-01-01

In this paper, the feasibility of microwave (MW) sintering PEEK (poly-ether-ether-ketone) based coatings was investigated. Three coatings were studied: pure PEEK, micron-SiC and nano-SiC particles filled (wt.10%) PEEK coatings. The results indicate that, for the two composite coatings, the SiC particles distributed in the polymer matrix, as a good MW susceptor, could be heated preferentially by MW radiation. Consequently, the polymer matrix was heated by these particles

Studies of flerovium and element 115 homologs with macrocyclic extractants

Science.gov (United States)

Despotopulos, John Dustin

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

Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

Energy Technology Data Exchange (ETDEWEB)

Fayolle-Guichard, F.

2005-04-01

Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

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.

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

Rearrangements of Cycloalkenyl Aryl Ethers

Directory of Open Access Journals (Sweden)

Mercedesz Törincsi

2016-04-01

Full Text Available Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

Ether: Bitcoin's competitor or ally?

OpenAIRE

Bouoiyour, Jamal; Selmi, Refk

2017-01-01

Although Bitcoin has long been dominant in the crypto scene, it is certainly not alone. Ether is another cryptocurrency related project that has attracted an intensive attention because of its additional features. This study seeks to test whether these cryptocurrencies differ in terms of their volatile and speculative behaviors, hedge, safe haven and risk diversification properties. Using different econometric techniques, we show that a) Bitcoin and Ether are volatile and relatively more resp...

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.

Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

NARCIS (Netherlands)

Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

2017-01-01

The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

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.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use

Directory of Open Access Journals (Sweden)

Denny Joseph Manual Kollareth

2018-03-01

Full Text Available Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [3H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [3H]cholesteryl oleoyl ether and [3H]cholesteryl hexadecyl ether from different suppliers, employing in vitro, in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro, in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments. Keywords: Cholesteryl ether, J774 A2 macrophages, Soy oil emulsion, Thin layer chromatography, triDHA emulsion

Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

Science.gov (United States)

Epov, Vladimir N

2011-08-07

A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

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.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

Science.gov (United States)

Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

2018-03-01

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

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...

Diaqua{6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne]diphenolato-κ2O,N,N′,O′}manganese(III perchlorate 18-crown-6 hemisolvate monohydrate

Directory of Open Access Journals (Sweden)

Ming-Ming Yu

2009-02-01

Full Text Available In the cation of the title compound, [Mn(C18H18N2O4(H2O2]ClO4·0.5C12H24O6·H2O, the MnIII ion is coordinated by two water O atoms, and two O atoms and two N atoms from the tetradentate 6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne]diphenolate ligand, completing a distorted octahedral geometry. One O atom of the 18-crown-6-ether is disordered over two positions with occupancies of 0.70 (2 and 0.30 (2.

Numerical investigation on the effect of injection pressure on the internal flow characteristics for diethyl ether, dimethyl ether and diesel fuel injectors using CFD

Directory of Open Access Journals (Sweden)

Vijayakumar Thulasi

2011-01-01

Full Text Available The spray characteristics of the diesel fuel are greatly affected by the cavitation formed inside the injector due to the high pressure differential across the nozzle. Many researchers across the globe are exploring the potential of using diethyl ether and dimethyl ether as an alternate for diesel fuel to meet the strict emission norms. Due to the variation in the fuel properties the internal flow characteristics in injectors for ether fuels are expected to be different from that of the diesel fuel. In this paper computational technique is used to study and compare the internal flow characteristics of diethyl ether, dimethyl ether and diesel fuel. The two phase flow model considering the fuel as a mixture of liquid and vapor is adopted for the simulation study. The injection pressure is varied from 100 to 400 bar and the flow characteristics of all three fuels are simulated and compared. Results indicate that all three fuels have distinct cavitating patterns owing to different property values. The dimethyl ether is found to be more cavitating than diesel and diethyl ether fuels as expected. The mass of fuel injected are found to be decreasing for the ether fuels when compared with diesel fuel at all injection pressures.

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.

New Calix[4]arene dibenzocrown ethers for selective sensing of cesium ion in aqueous environment

International Nuclear Information System (INIS)

Kim, Jong Seung; Kim, Jong Kuk; Choi, Wang Kyu; Lee, Kune Woo; Oh, Won Jin

1997-01-01

1,3-dialkoxycalix[4]arene dibenzocrown ethers (6-9) were successfully synthesized in the fixed 1,3-alternate conformation with over 90% yields by the reaction of corresponding 1,3dialkoxycalix[4]arenes 2-5 with dibenzodimesylate 13 in acetonitrile as a solvent in the presence of cesium carbonate as a base. In view of cyclization yield, the use of dimesylate is found to be better than that of dibenzoditosylate. With an unusual AB pattern in 1 H NMR spectrum for compound 9, it is suggested that conformational structure of 1,3-diallyloxycalix[4]arene dibenzocrown ether be less flexible than that of usual 1,3-alternate calixcrown ether, probably due to steric effects of two ally1 group. Complexation of the corresponding calix[4]arene 6-9 toward alkali metal ions using single flux method through bulk liquid membrane system was found to give a high cesium selectivity. 28 refs., 1 tab., 1 fig

New Calix[4]arene dibenzocrown ethers for selective sensing of cesium ion in aqueous environment

Energy Technology Data Exchange (ETDEWEB)

Kim, Jong Seung; Kim, Jong Kuk [Konyang University, Nonsan (Korea, Republic of); Choi, Wang Kyu; Lee, Kune Woo; Oh, Won Jin [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1997-12-31

1,3-dialkoxycalix[4]arene dibenzocrown ethers (6-9) were successfully synthesized in the fixed 1,3-alternate conformation with over 90% yields by the reaction of corresponding 1,3dialkoxycalix[4]arenes 2-5 with dibenzodimesylate 13 in acetonitrile as a solvent in the presence of cesium carbonate as a base. In view of cyclization yield, the use of dimesylate is found to be better than that of dibenzoditosylate. With an unusual AB pattern in {sup 1}H NMR spectrum for compound 9, it is suggested that conformational structure of 1,3-diallyloxycalix[4]arene dibenzocrown ether be less flexible than that of usual 1,3-alternate calixcrown ether, probably due to steric effects of two ally1 group. Complexation of the corresponding calix[4]arene 6-9 toward alkali metal ions using single flux method through bulk liquid membrane system was found to give a high cesium selectivity. 28 refs., 1 tab., 1 fig.

AIRBORNE POLYBROMINATED DIPHENYL ETHERS IN A COMPUTER CLASSROOM OF COLLEGE IN TAIWAN

Directory of Open Access Journals (Sweden)

F. H. Chang ، C. R. Yang ، C. Y. Tsai ، W. C. Lin

2009-04-01

Full Text Available This study characterized the airborne exposure of students to thirty polybrominated diphenyl ether congeners inside and outside a computer classroom in a southern Taiwan college. Arithmetic mean values of total indoor and outdoor polybrominated diphenyl ether concentrations were 125.0 pg/m3 (89.8 to 203.9 pg/m3 and 110.3 pg/m3 (83.5 to 157.0 pg/m3, respectively. Total indoor polybrominated diphenyl ether concentrations were one order of magnitude lower than those detected in homes in Birmingham, United Kingdom and in Ottawa, Canada but were several times higher than those measured in the ambient air in Ottawa, Canada and from the Bohai Sea to the Arctic. The five highest indoor concentrations of polybrominated diphenyl ether congeners were decabromodiphenyl ether (23.0 pg/m3, 4,4’-dibromodiphenyl ether (15.9 pg/m3, 2,2’,3,4,4’,5,5’,6-octabromodiphenyl ether (10.6 pg/m3, 2,4-dibromodiphenyl ether (10.3 pg/m3 and 2,2’,3,4,4’,5’,6-heptabromodiphenyl ether (10.0 pg/m3. Although indoor and outdoor total polybrominated diphenyl ether concentrations did not significantly differ, the indoor concentrations of 2,4-dibromodiphenyl ether, 2,2’,4-tribromodiphenyl ether, 2,4,4’-tribromodiphenyl ether, 2,2’,4,5’-tetrabromodiphenyl ether and 2,3’,4’,6-tetrabromodiphenyl ether were significantly higher than their outdoor concentrations. This study suggests the following measures: 1 to increase the air exchange rate and open classroom doors and windows for several minutes before classes to reduce indoor PBDE concentrations; 2 to reduce polybrominated diphenyl ether emissions from new devices, it’s better to use computer-related products that meet the Restriction of Hazardous Substances Directive adopted by the European Union.

Thermally reversible cross-linked poly(ether-urethanes

Directory of Open Access Journals (Sweden)

V. Gaina

2013-07-01

Full Text Available Cross-linked poly(ether-urethanes were prepared by Diels-Alder (DA reaction of the furan-containing poly(ether-urethane to bismaleimides and showed thermal reversibility evidenced by differential scanning calorimetry and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR. The furan-containing poly(ether-urethanes were synthesized by the polyaddition reaction of 1,6-hexamethylene diisocyanate (HMDI or 4,4'- dibenzyl diisocyanate (DBDI to poly(tetramethylene ether glycol (PTMEG having Mn = 250, 650, 1000, 1500 and 2000 and 2-[N,N-bis(2-methyl-2-hydroxyethylamino]furfuryl as chain extender by the solution prepolymer method. The molar ratio of isocyanate: PTMEG:chain extender varied from 2:1:1 to 4:1:3, which produces a molar concentration of furyl group ranging between 3.65•10–4 and 1.25•10–3 mol/g.

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.

Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

OpenAIRE

Koziara, Beata; Kappert, Emiel; Ogieglo, Wojciech; Nijmeijer, Dorothea C.; Hempenius, Mark A.; Benes, Nieck Edwin

2016-01-01

Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material, most likely via a slight cross-linking by H-substitution. It is well-known that the sulfonate proton plays a major role in the desulfonation reactions, and exchanging the protons with other cations ...

[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.

How protein recognizes ladder-like polycyclic ethers. Interactions between ciguatoxin (CTX3C) fragments and its specific antibody 10C9.

Science.gov (United States)

Ui, Mihoko; Tanaka, Yoshikazu; Tsumuraya, Takeshi; Fujii, Ikuo; Inoue, Masayuki; Hirama, Masahiro; Tsumoto, Kouhei

2008-07-11

Ciguatoxins are a family of marine toxins composed of transfused polycyclic ethers. It has not yet been clarified at the atomic level on the pathogenic mechanism of these toxins or the interaction between a polycyclic ether compounds and a protein. Using the crystal structures of anti-ciguatoxin antibody 10C9 Fab in ligand-free form and in complexes with ABCD-ring (CTX3C-ABCD) and ABCDE-ring (CTX3C-ABCDE) fragments of the antigen CTX3C at resolutions of 2.6, 2.4, and 2.3 angstroms, respectively, we elucidated the mechanism of the interaction between the polycyclic ethers and the antibody. 10C9 Fab has an extraordinarily large and deep binding pocket at the center of the variable region, where CTX3C-ABCD or CTX3C-ABCDE binds longitudinally in the pocket via hydrogen bonds and van der Waals interactions. Upon antigen-antibody complexation, 10C9 Fab adjusts to the antigen fragments by means of rotational motion in the variable region. In addition, the antigen fragment lacking the E-ring induces a large motion in the constant region. Consequently, the thermostability of 10C9 Fab is enhanced by 10 degrees C upon complexation with CTX3C-ABCDE but not with CTX3C-ABCD. The crystal structures presented in this study also show that 10C9 Fab recoginition of CTX3C antigens requires molecular rearrangements over the entire antibody structure. These results further expand the fundamental understanding of the mechanism by which ladder-like polycyclic ethers are recognized and may be useful for the design of novel therapeutic agents by antibodies, marine toxins, or new diagnostic reagents for the detection and targeting of members of the polycyclic ether family.

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

Calcium isotope fractionation in liquid chromatography with benzo-18-crown-6 resin in aqueous hydrobromic acid medium

International Nuclear Information System (INIS)

Sato, Takuya; Oi, Takao

2015-01-01

Liquid chromatography operated in a breakthrough mode was employed to study calcium isotope fractionation in the aqueous hydrobromic acid medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of calcium was observed in the frontal part of respective calcium chromatograms. The values of the isotope fractionation coefficient were on the order of 10 -3 . The observed isotope fractionation coefficient was dependent on the concentration of hydrobromic acid in the calcium feed solution; a higher HBr concentration resulted in a smaller fractionation coefficient value. The present calcium isotope effects were most probably mass-dependent, indicating that they mostly came from isotope effects based on molecular vibration. Molecular orbital calculations supported the present experimental results in a qualitative fashion. Chromatography operated in aqueous HBr media is a better system of Ca isotope separation than that operated in aqueous HCl media. (author)

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.

Dimethyl ether as a drift-chamber gas

International Nuclear Information System (INIS)

Bari, G.; Basile, M.; Bonvicini, G.; Cara Romeo, G.; Casaccia, R.; Cifarelli, L.; Cindolo, F.; Contin, A.; D'Ali, G.; Del Papa, C.; Focardi, S.; Iacobucci, G.; Maccarrone, G.; Massam, T.; Motta, F.; Nania, R.; Palmonari, F.; Prisco, G.; Sartorelli, G.; Susinno, G.; Votano, L.; Zichichi, A.; Istituto Nazionale di Fisica Nucleare, Bologna; European Organization for Nuclear Research, Geneva; Istituto Nazionale di Fisica Nucleare, Frascati; Michigan Univ., Ann Arbor; Palermo Univ.

1986-01-01

We have continued the testing of dimethyl ether as a drift-chamber gas in order to improve the understanding of its properties. In particular, we report on measurement accuracy, on systematic effects, and some preliminary data on the ageing of a detector filled with dimethyl ether. (orig.)

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

Science.gov (United States)

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

2015-07-14

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

Process for making propenyl ethers and photopolymerizable compositions containing them

Science.gov (United States)

Crivello, James V.

1996-01-01

Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

Science.gov (United States)

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

Distribution of strontium in DB18K6 and DTBDB18K6 systems

International Nuclear Information System (INIS)

Usarov, Z.O.; Khujaev, S.

2007-01-01

Distributions of strontium in DB18K6 and DTBDB18K6 crown-ethers in chloroform were investigated for extraction of strontium from water solutions of nitric acid. Nitrate solutions with various pH were considered. In both crown-ethers the most extraction of strontium was observed for the moderate pH values. Equilibrium of extraction process is reached for comparatively short time and is occurred to be 20 min (authors)

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

Energy Technology Data Exchange (ETDEWEB)

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

1999-11-01

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

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

International Nuclear Information System (INIS)

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

1999-01-01

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

Preparation, characterization and in vitro dissolution study of Nitrazepam: Cyclodextrin inclusion complex

OpenAIRE

Patel, J. S.; Patel, R. P.

2012-01-01

The objectives of this research were to prepare and characterize inclusion complexes of Nitrazepam with Hydroxypropyl-β-cyclodextrin (HPβCD) and Sulfobutyl ether β-cyclodextrin (SBEβCD) to study the effect of complexation on the dissolution rate of Nitrazepam, a water-insoluble drug. The phase solubility profile of Nitrazepam with Hydroxypropyl- β-cyclodextrin and Sulfobutyl ether β-cyclodextrin was an AP-type, indicating the formation of 2:1 stoichiometric inclusion complexes. Gibbs free ene...

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.

The adsorption of Tl(I), Au(III), Cu(II) and the separation of 199Tl from alpha bombardment of gold target with PDB-18C6

International Nuclear Information System (INIS)

Zhou Dehai; Zhou Jimeng

1989-01-01

The adsorptive behavior of polymer of methyl aldehyde of dibenzo-18-crown-6 (PDB-18C6) in hydrochloric acid medium is studied and it is shown that the adsorption of T1(I), Au(III), and Cu(II) depends on the particle size of the crown ether resins, hydrochloric acid concentration and amount of the crown ether resins used. The difference in the adsorption behavior of different particle sizes of crown ether resins may be used for separating Tl(I), Au(III), and Cu(II) ions. The best eluant of Tl(I) and Au(III) is 0.4 mol/l perchloric acid and 2-ethoxy-ethanol. The recovery for Tl(I) is 82-98.8%. The gold target is bombarded in a 1.2 m cyclotron with 25-27 MeV α-particle with a cumulative beam intensities of 27μA·h, and 199 Tl is separated from the gold target with PDB-18C6. γ-spectrometry has shown that the Tl obtained is 199 Tl of high purity containing only about 0.50% 200 Tl

Radiation-induced transformations of cellulose ethers

International Nuclear Information System (INIS)

Nud'ga, L.A.; Petropavlovskii, G.S.; Plisko, E.A.; Isakova, O.V.; Ershov, B.G.

1988-01-01

The purpose of this investigation was to study the transformation which take place under the action of γ-radiation in a number of cellulose ethers containing both saturated (carboxymethyl, hydroxyethyl) and unsaturated (allyl, methacryloyl) groups. Irradiation was carried out on a 60 Co unit in air at 77 and 300 K; the dose rate was 37 and 50 kGy/h respectively. The EPR spectra of γ-irradiated hydroxyethyl- and allylhydroxyethylcelluloses are identical. Under the action of γ-radiation extensive changes took place in cellulose ethers which are exhibited in degradation or the formation of three-dimensional structures and are accompanied by a change in the functional composition. The efficiency in the formation of radicals and their localization are determined by the nature and number of substituents in the cellulose ethers

Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

Energy Technology Data Exchange (ETDEWEB)

T.A. Semelsberger

2004-10-01

The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

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)

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

International Nuclear Information System (INIS)

Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

2017-01-01

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

2017-02-15

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

2H isotope effect on 13C chemical shifts of Nitro-Benzo-9-Crown-3

International Nuclear Information System (INIS)

Moghimi, A.; Rastegar, M.; Ghandi, M.; Bijanzadeh, H. R.

2002-01-01

Deuterium substitution on two ortho-substituted-OCH 2 fragments in Nitro-Benzo-9 Crown-3 induces low frequency shifts, positive m ''nΔC j, in all 13 C NMR resonances which is an indication of the increased shielding in this crown ether. The magnitude of these shifts vary from 15 ΔC 7=716 to 54 ΔC 3=15 ppb for C 7 and C 3 carbons directly attached to 2 H, respectively. The influences of concentration and solvent, CDCl 3 CD 3 COCD 3 , and C 6 D 6 , on mn ΔC j values were investigated. The mn ΔC j values depended more on the nature of the solvent than on the concentration. The order of induced isotope shifts is 15 Δ, 51 Δ > 24 Δ, 42 Δ> 34 Δ, 43 Δ > 56 Δ, 65 Δ> 45 Δ, 54 Δ. The isotope shifts observed are suggested to be a sum of contributions from low frequency shift due to inductive-type and negative hyperconjugation perturbations. The C-D bond, as a poorer electron acceptor than a C-H bond induced less positive charge on directly attached oxygens O 1 and O 2. This, in turn, causes shielding of C 1 and C 2 in C1O1CD 2 and C 2 0 2 CD 2 fragments. The difference in 34 ΔC 1 and 43 ΔC 2 values is attributed to the conformational dependence of the negative hyperconjugation. The C 1 and C 2, are in fact, not equally affected by the two CD 2 groups by negative hyperconjugation because of the existence of NO 2 group attached to the benzene ring

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.

On the ether-like Lorentz-breaking actions

International Nuclear Information System (INIS)

Petrov, A.Yu; Nascimento, J.R.; Gomes, M.; Silva, A. J. da

2011-01-01

We demonstrate the generation of the CPT-even, ether-like Lorentz-breaking actions for the scalar and electro-magnetic fields via their appropriate Lorentz-breaking coupling to spinor fields in three, four and five space-time dimensions. Besides, we show that the ether-like terms for the spinor field also can be generated as a consequence of the same couplings. The key result which will be presented here is the finiteness of the ether-like term for the electromagnetic field not only in three and five space-time dimensions where it is natural due to known effects of the dimensional regularization but also in four space-time dimensions. Moreover, we present the calculation of the last result within different calculational schemes and conclude that the result for the four-dimensional ether-like term for the electromagnetic field essentially depending on the calculation scheme, similarly to the result for the Carroll-Field-Jackiw (CFJ) term which probably signalizes a possibility for arising of a new anomaly. Also we discuss the dispersion relations in the theories with ether-like Lorentz-breaking terms which allows to discuss the consistency of the Lorentz-breaking modified theories for different (space-like or time-like) Lorentz-breaking vectors and find the tree-level effective (Breit) potential for fermion scattering and the one-loop effective potential corresponding to the action of the scalar field. (author)

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

Science.gov (United States)

Korchev, A S; Shulyak, T S; Slaten, B L; Gale, W F; Mills, G

2005-04-28

Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.

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...

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.

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)

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...

Thermogravimetric analysis of the polymer acrylate-vinyl ether mixture cured by radiation

International Nuclear Information System (INIS)

Danu, Sugiarto

1998-01-01

An experiment on thermal stability of the polymer acrylate-vinyl ether mixture cured by radiation have been done using thermogravimetric analysis. Three kinds of acrylic oligomers i.e., epoxy acrylate, urethane acrylate, and polypropylene glycol diacrylate, and vinyl ether monomers i.e., triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexane dimethanol divinyl ether (CHVE), and butanediol monovinyl ether (HBVE) were used in the experiment. Reaction was taken via radical and cationic polymerisation. In case of cationic polymerisation, diphenyliodonium hexafluorophosphate fotoinisiator was used in the formulation. Thermogravimetric analysis was conducted in a nitrogen atmosphere at a flow rate of 40 ml/minute with a constant heating rate 10 o C and evaluation range were done from 25 to 500 o C. The results of thermogravimetric analysis showed that acrylate and DVE-3 mixture produced the polymer films with higher thermal stability than the mixture of acrylate with CHVE or HBVE. The composition of acrylate-vinyl ether mixture and degree of unsaturation of vinyl ether monomers influenced the thermal stability of polymer. The mixture of epoxy acrylate-vinyl ether and polypropylene glycol diacrylate-vinyl ether have 1 initial decomposition temperature whereas the urethane acrylate-vinyl ether mixture has 2 initial decomposition temperatures. (authors)

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 ...

DETERMINATION OF SURFACTANT SODIUM LAURYL ETHER SULFATE BY ION PAIRING CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY DETECTION

Science.gov (United States)

A method for the determination of the anionic Steol CS-330 surfactant is described. CS-330 is a complex mixture of oligomers due to the various sizes of fatty alcohols and the number of moles of the ethoxylation. The main component of CS-330 is sodium lauryl ether sulfate (SLES)....

Analysis of metals in solution using electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Van Berkel, G.J.; McLuckey, S.A.; Glish, G.L.

1991-01-01

Electrospray ionization-mass spectrometry (ES-MS) has gained most of its recent attention because of the ability to produce multiply charged ions from very large biomolecules making them amenable to analysis by most modern mass spectrometers. However, ES-MS is equally well suited for compounds of low or moderate molecular weight that are difficult to volatilize intact by others methods. Moreover, the early work of Fenn and co-workers (1,2) and recent reports by Kebarle and co-workers (3,4) attest to the applicability of ES-MS to the study of the gas-phase chemistry of multiply solvated or coordinated metal ions. The utility of ES-MS for the analysis of metals in solution derives in part from the facility with which the metal ions are solvated by or form complexes with the ES solvent or other reagents added to the solvent. Solvation and complexation can be a hindrance, however, in the analytical application of ES-MS to the analysis of metals in solution, especially solutions of metals in water. The data presented here demonstrate that many of the problems in the ES-MS analysis of metals can be overcome by complexing the metals with crown ethers and/or extracting the metals from water into an organic phase using crown ethers. 5 refs., 4 figs

Study by infrared spectroscopy of coordination compounds of some ethers with aluminium chloride and bromide

International Nuclear Information System (INIS)

Derouault, Jean

1968-01-01

After having recalled some thermodynamic aspects related to electron donor-acceptor compounds, this research thesis reports the study of infrared spectra of 1-1R 2 O-AlX 3 complexes in a condensed state (X is either bromine or chlorine). The next part reports the study of infrared spectra of 2-1(R 2 O) 2 -AlX 3 complexes in a condensed state (X is also either bromine or chlorine), and the third part addresses the study of the formation of complexes of aluminium halides with ethers, in a dissolved state

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.

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.

Exogenous ether lipids predominantly target mitochondria

DEFF Research Database (Denmark)

Kuerschner, Lars; Richter, Doris; Hannibal-Bach, Hans Kristian

2012-01-01

Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high......, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria...

Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

International Nuclear Information System (INIS)

Silva, V.S.; Ruffmann, B.; Vetter, S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M.; Nunes, S.P.

2006-01-01

Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion[reg] 112 was used as reference material. DMFC tests were also performed at 50 deg. C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion[reg] 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion[reg] 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%

Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

Energy Technology Data Exchange (ETDEWEB)

Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

2011-01-01

Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

Analysis of electron-irradiated poly-ether ether ketone by X-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Oyabu, Matashige; Kobayashi, Yoshinori; Seguchi, Tadao; Sasuga, Tsuneo; Kudoh, Hisaaki.

1995-01-01

Organic polymers used in atomic power plants or space are damaged by ionizing irradiation. Radicals produced by irradiation cause oxidation, chain scission and crosslinking, all of which lead to degradation of the material. In this paper, the surface of electron-irradiated poly-ether ether ketone (PEEK) was studied by X-ray photoelectron spectroscopy (XPS). The irradiation in air was found to oxidize the PEEK surface producing carboxyl groups, the content of which dependant on the dose. Carboxyl groups were not produced in helium gas. Quantitative spectral analysis indicated that the aromatic structure might be decomposed. Some comparison was made between the semicrystalline and amorphous samples. The oxygen content resulting from irradiation, of semicrystalline PEEK increased more than that of amorphous PEEK. (author)

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

Application of simplified PC-SAFT to glycol ethers

DEFF Research Database (Denmark)

Avlund, Ane Søgaard; Kontogeorgis, Georgios; Michelsen, Michael Locht

2012-01-01

The simplified PC-SAFT (sPC-SAFT) equation of state is applied for binary glycol ether-containing mixtures, and it is investigated how the results are influenced by inclusion of intramolecular association in the association theory. Three different glycol ethers are examined: 2-methoxyethanol, 2...

Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

International Nuclear Information System (INIS)

Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

2014-01-01

Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

Energy Technology Data Exchange (ETDEWEB)

Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang, E-mail: wolfgang.bacsa@cemes.fr [CEMES-CNRS and University of Toulouse, 29 Jeanne Marvig, 31055 Toulouse (France); Boyer, François; Olivier, Philippe [Université de Toulouse, Institut Clément Ader, I.U.T. Université Paul Sabatier - 133C Avenue de Rangueil - B.P. 67701, 31077 Toulouse CEDEX 4 (France); Sapelkin, Andrei [School of Physics and Astronomy, Queen Mary, University of London, Mile End Road, E1 4NS London (United Kingdom); King, Stephen; Heenan, Richard [ISIS Facility, Rutherford Appleton Laboratory, Chilton, OX11 0QX Didcot (United Kingdom); Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri [AIRBUS FRANCE (B.E. M and P Toulouse), 316 Route de Bayonne, 31060 Toulouse (France)

2014-06-21

Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

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...