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

NASA Astrophysics Data System (ADS)

Furmanova, N. G.; Rabadanov, M. Kh.; Chernaya, T. S.; Fonari, M. S.; Simonov, Yu. A.; Ganin, É. V.; Gelmboldt, V. O.; Grigorash, R. Ya.; Kotlyar, S. A.; Kamalov, G. L.

2008-03-01

Two isostructural complexes of dioxonium [H5O2]+ with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 · H5O2)][TaF6] ( I) and [(tetrabenzo-30-crown-10 · H5O2)][NbF6] ( 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) Å, b = 15.2259(13) Å, c = 16.4473(13) Å, and β = 99.398(6)° for complex I and a = 15.7117(12) Å, b = 15.2785(15) Å, c = 16.5247(15) Å, and β = 99.398(7)° for complex II. These complexes belong to the ionic type. The dioxonium cation [H5O2]+ in the form of the two-unit cluster [H3O · H2O]+ is stabilized by the strong hydrogen bond OH⋯O [O⋯O, 2.353(4) Å] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O⋯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⋯F type.

Recent Advanced in Rare Earth Chemistry: IREC (International Rare Earth Conference) 85 Held at Zurich (Switzerland) on 4-8 Mar 85.

DTIC Science & Technology

1985-06-04

compounds were employed since 1979. The polyfunc- studied using time-resolved spectro- tlonal ligands (L) included crown ethers scopy, and the...structure of rare earth * Aqueous complexes with cyclic poly - compounds (for example Cs3Ln2X9), was ethers crown ethers , Alstad, Univer- presented by A...Approved for public release; distribution unlimited U.S. Office of Naval Research, London ag - ’ 3 k) I 5.’ - ~1 I 9 ’<I. A -i I. 4. -A kA IS7 ASS

The influence of water-ethanol mixture on the thermodynamics of complex formation between 18-crown-6 ether and L-phenylalanine

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Sharnin, V. A.; Chernov, I. V.; Matteoli, E.; Terekhova, I. V.; Kumeev, R. S.

2012-08-01

The influence of water-ethanol mixture composition on the complex formation between 18-crown-6 ether and L-phenylalanine was studied by titration calorimetry at Т = 298.15 K. The standard thermodynamic parameters (ΔrGо, ΔrHо, ТΔrSо) of formation of [Phe18C6] molecular complex were calculated from data obtained by means of the microcalorimetric system TAM III (TA Instruments, USA) at X(EtOH) = 0.0/0.6 mol fraction. The stability of [Phe18C6] and the mechanism of complexation in water were investigated using the 1Н and 13С NMR spectroscopy. The increase of EtOH concentration results in an increase of the complex stability and of the exothermicity of complexation.

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

PubMed

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 be predicted on the basis of the derived stability constants for the individual [2]pseudorotaxanes.

Crown ethers in graphene

DOE PAGES

Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; ...

2014-11-13

Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

Temperature-dependent IR spectroscopic and structural study of 18-crown-6 chelating ligand in the complexation with sodium surfactant salts and potassium picrate.

PubMed

Mihelj, Tea; Tomašić, Vlasta; Biliškov, Nikola; Liu, Feng

2014-04-24

18-crown-6 ether (18C6) complexes with the following anionic surfactants: sodium n-dodecylsulfate (18C6-NaDS), sodium 4-(1-pentylheptyl)benzenesulfonate (18C6-NaDBS); and potassium picrate (18C6-KP) were synthesized and studied in terms of their thermal and structural properties. Physico-chemical properties of new solid 1:1 coordination complexes were characterized by infrared (IR) spectroscopy, thermogravimetry and differential thermal analysis, differential scanning calorimetry, X-ray diffraction and microscopic observations. The strength of coordination between Na(+) and oxygen atoms of 18C6 ligand does not depend on anionic part of the surfactant, as established by thermodynamical parameters obtained by temperature-dependent IR spectroscopy. Each of these complexes exhibit different kinds of endothermic transitions in heating scan. Diffraction maxima obtained by SAXS and WAXS, refer the behavior of the compounds 18C6-NaDS and 18C6-NaDBS as smectic liquid crystalline. Distortion of 18C6-NaDS and 18C6-KP complexes occurs in two steps. Temperature of the decomplexation of solid crystal complex 18C6-KP is considerably higher than of mesophase complexes, 18C6-NaDS, and 18C6-NaDBS. The structural and liquid crystalline properties of novel 18-crown-ether complexes are function of anionic molecule geometry, type of chosen cation (Na(+), K(+)), as well as architecture of self-organized aggregates. A good combination of crown ether unit and amphiphile may provide a possibility for preparing new functionalized materials, opening the research field of ion complexation and of host-guest type behavior. Copyright © 2013 Elsevier B.V. All rights reserved.

Aza compounds as anion receptors

DOEpatents

Lee, H.S.; Yang, X.Q.; McBreen, J.

1998-01-06

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

Aza compounds as anion receptors

DOEpatents

Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

1998-01-06

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

DOEpatents

Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

1999-01-01

A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

DOEpatents

Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

1999-03-30

A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

Crown ether stereoisomerism: Implications in metal ion extraction and ionic liquid design

NASA Astrophysics Data System (ADS)

Pawlak, Alan J.

Since their discovery more than four decades ago, crown ethers (CEs) have been the subject of intense investigation in a number of fields. Although many of the structural features that govern the behavior of these compounds have been thoroughly explored, the effect of their stereochemistry has received relatively little attention. In the present work, crown ether stereochemistry is shown to have important implications in both the design of ternary (i.e., three-component) ionic liquids (TILs) and metal ion extraction. Specifically, as a first step toward the development of guidelines for the rational design of ternary ionic liquids employing crown ethers as the neutral extractant, a systematic examination of the effect of crown ether stereochemistry (employing dicyclohexano-18-crown-6 (DCH18C6) as a representative crown compound), along with ring size, the nature and number of donor atoms, and the presence of functional groups, on the thermal properties (i.e., melting point or glass transition; decomposition or evaporation) of these compounds was carried out. Stereochemistry was found to have no appreciable impact on the onset temperature for mass loss. Rather, molecular weight and aromaticity were found to be more influential. Stereochemistry was, however, found to significantly affect the melting point of a TIL prepared from it; while the metal-CE formation constant, which varies with stereoisomer was observed to determine the onset temperature for mass loss of the TIL. To explore the implications of crown ether stereoisomerism in metal ion extraction, the formation constants for alkaline earth cation complexes with the isomers of DCH18C6 and selected stereoisomers of di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6) were measured. These values were found to vary inversely with the ligand strain (i.e., reorganizational) energy for the isomer, as determined by molecular mechanics calculations. Using this relationship (along with additional identification methods), three isomers of DtBuCH18C6, which were separated by preparative LC, were definitively identified. Three additional isomers were partially identified.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Furmanova, N. G., E-mail: furm@ns.crys.ras.ru; Rabadanov, M. Kh.; Chernaya, T. S.

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} =more » 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.« less

Anion receptor compounds for non-aqueous electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

2000-09-19

A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

DOE PAGES

Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; ...

2014-04-23

Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

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

NASA Astrophysics Data System (ADS)

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.

Electron spin resonance and proton matrix electron nuclear double resonance studies of N,N,N[prime],N[prime]-tetramethylbenzidine photoionization in sodium and lithium dodecyl sulfate micelles: Structural effects of crown ethers

DOE Office of Scientific and Technical Information (OSTI.GOV)

McManus, H.J.D.; Young Soo Kang; Kevan, L.

1993-01-07

The study of model membrane systems enjoys increasing attention within the area of solar energy research. An electron nuclear double resonance and electron spin resonance study of photogenerated N,N,N[prime],N[prime]-tetramethylbenzidine (TMB) cation in frozen suspensions of lithium (LDS) and sodium (SDS) dodecyl sulfate micelles containing various concentrations of cyclic polyethers was undertaken. The relative location of the TMB cation within the organic aggregate was determined from the proton matrix ENDOR line width at 142 K. A broader line width was observed in LDS compared to SDS micelles, which is due to the fact that the larger lithium cation opens the micellarmore » interface resulting in increased hydration and deeper solubilization of TMB. The proton matrix ENDOR line width decreased upon addition of crown ethers. This decrease may be explained by displacement of the TMB toward the interface as a result of the decrease in ionic strength caused by the complexation of the countercations. The photoyield shows a slight increase with addition of crown ethers. This increase is most likely caused by the increase in the effective anionic charge of the micelle effected by the complexation of the sodium or lithium ions by the crown ethers. This increase in the anionic charge mitigates the rate of thermal back electron transfer resulting in an increased photoyield. 54 refs., 6 figs., 2 tabs.« less

Ultrasound promoted N-alkylation of pyrrole using potassium superoxide as base in crown ether.

PubMed

Yim, E S; Park, M K; Han, B H

1997-04-01

Ultrasound accelerates the N-alkylation of pyrrole by alkylating reagents using potassium superoxide as base in the presence of 18-crown-6. A much lower yield of N-alkylated pyrrole was realized in the absence of ultrasound. N-alkylating reagents employed for pyrrole are methyl iodide, ethyl bromide, benzyl bromide, as well as acrylonitrile allyl cyanide and methyl acrylate. In an extension of this work, we have found that ultrasound was not necessary for the N-alkylation of indole and alkyl amine, such as diphenyl amine and piperidine with alkyl halides using our reagents. In all cases we observed that the 18-crown-6 catalyzed N-alkylation reaction gives higher yields of N-alkylated products than that without crown ether, when potassium superoxide was used as base. These observations are probably due to the potassium-crown complex which can be released when the reaction goes to completion.

Capillary electrophoresis separation of peptide diastereomers that contain methionine sulfoxide by dual cyclodextrin-crown ether systems.

PubMed

Zhu, Qingfu; Heinemann, Stefan H; Schönherr, Roland; Scriba, Gerhard K E

2014-12-01

A dual-selector system employing achiral crown ethers in combination with cyclodextrins has been developed for the separation of peptide diastereomers that contain methionine sulfoxide. The combinations of the crown ethers 15-crown-5, 18-crown-6, Kryptofix® 21 and Kryptofix® 22 and β-cyclodextrin, carboxymethyl-β-cyclodextrin, and sulfated β-cyclodextrin were screened at pH 2.5 and pH 8.0 using a 40/50.2 cm, 50 μm id fused-silica capillary and a separation voltage of 25 kV. No diastereomer separation was observed in the sole presence of crown ethers, while only sulfated β-cyclodextrin was able to resolve some peptide diastereomers at pH 8.0. Depending on the amino acid sequence of the peptide and the applied cyclodextrin, the addition of crown ethers, especially the Krpytofix® diaza-crown ethers, resulted in significantly enhanced chiral recognition. Keeping one selector of the dual system constant, increasing concentrations of the second selector resulted in increased peak resolution and analyte migration time for peptide-crown ether-cyclodextrin combinations. The simultaneous diastereomer separation of three structurally related peptides was achieved using the dual selector system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

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

PubMed

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.

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

PubMed

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(5) were reached for the devices of triple-decker compound 1 deposited on the OTS-treated SiO(2)/Si substrates, indicating the effect of substrate surface treatment on the OFET performance due to the improvement on the film quality as demonstrated by the atomic force microscope investigation results.

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

DOE PAGES

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi; ...

2015-10-26

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

SYNTHESIS OF NOVEL CROWN ETHERS BEARING THE exo-cis-2,3-NORBORNYL GROUP AS POTENTIAL Na+ AND K+ EXTRACTANTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robeson, R.M.; Bonnesen, P.

2007-01-01

The synthesis of a series of novel dinorbornyl-16-crown-5 and dinorbornyl-18-crown-6 ethers that incorporate the exo-cis-2,3-norbornyl moiety within the macrocycle framework is described. The key starting material for the crown ethers, exo-cis-2,3-norbornanediol, was successfully prepared on a large (>30g) scale in 88% yield from norbornylene by osmium tetroxide-catalyzed hydroxylation. The syn and anti isomers of the dinorbornyl-16-crown-5 ether family were prepared using diethylene glycol with ring closure achieved using a methallyl linkage. The isomers cis-syn-cis and cis-anti-cis di-norbornano-15-methyleno-16-crown-5 (6A and 6B) could be separated using column chromatography, and a single crystal of the syn isomer 6A suitable for X-ray crystal structuremore » analysis was obtained, thereby confi rming the syn orientation. The syn and anti isomers of the dinorbornyl-18-crown-6 ether family were successfully prepared employing a different synthetic strategy, involving the potassium–templated cyclization of two bis-hydroxyethoxy-substituted exo-cis-2,3-norbornyl groups under high dilution conditions. Attempts to fully separate cis-syn-cis di-norbornano-18-crown-6 (10A) and cis-anti-cis di-norbornano-18-crown-6 (10B) from one another using column chromatography were unsuccessful. All intermediates and products were checked for purity using either thin layer chromatography or gas chromatography, and characterized by proton and carbon NMR. Crown ethers 6AB and 10AB are to our knowledge the fi rst crown ethers to incorporate the exo-cis-2,3-norbornyl moiety into the crown ring to be successfully synthesized and characterized.« less

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

PubMed

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.

Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fonari, M. S.; Alekseeva, O. A.; Furmanova, N. G.

2007-03-15

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][TaF{sub 6}] and [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) A, b = 11.947(5) A, c = 27.392(12) A, {beta} = 93.11(1) deg., Z = 4, and space group P2{sub 1}/n for modification I; and a = 10.828(1) A, b = 11.204(1) A, c = 12.378(1) A, {alpha} = 72.12(1) deg., {beta} = 79.40(1) deg., {gamma} = 73.70(1) deg.,more » Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] (III) with the unit cell parameters a = 10.796(3) A, b = 11.183(3) A, c = 12.352(3) A, {alpha} = 72.364(5) deg., {beta} = 79.577(5) deg., {gamma} = 73.773(4) deg., Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I-III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48-2.58 A). The conformation of the macrocycle in complex I differs substantially from that in complex II (III)« less

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel.

PubMed

Kumar, Amit; Lionetti, Davide; Day, Victor W; Blakemore, James D

2018-01-02

Assembly of heterobimetallic complexes is synthetically challenging due to the propensity of ditopic ligands to bind metals unselectively. Here, we employ a novel divergent approach for selective preparation of a variety of bimetallic complexes within a ditopic macrocyclic ligand platform. In our approach, nickel is readily coordinated to a Schiff base cavity, and then a range of redox-inactive cations (M=Na + , Ca 2+ , Nd 3+ , and Y 3+ ) are installed in a pendant crown-ether-like site. This modular strategy allows access to complexes with the highly Lewis acidic trivalent cations Nd 3+ and Y 3+ , a class of compounds that were previously inaccessible. Spectroscopic and electrochemical studies reveal wide variations in properties that are governed most strongly by the trivalent cations. Exposure to dimethylformamide drives loss of Nd 3+ and Y 3+ from the pendant crown-ether site, suggesting solvent effects must be carefully considered in future applications involving use of highly Lewis acidic metals. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Change in the Gibbs energy of 18-crown-6 ether transfer from methanol to methanol-acetonitrile mixtures at 298 K

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Usacheva, T. R.; Kuz'mina, K. I.; Volkova, M. A.; Sharnin, V. A.

2015-01-01

The Gibbs energies of the transfer of 18-crown-6 ether from methanol to its mixtures with acetonitrile (χAN = 0.0-1.0 mole fraction) are determined by means of interphase distribution at 298 K. The effect the solvent composition has on the thermodynamic characteristics of the solvation of 18-crown-6 ether is analyzed. An increase in the content of acetonitrile in the mixed solvent enhances the solvation of crown ether due to changes in the energy of the solution. Resolvation of the macrocycle is assumed to be complete at acetonitrile concentrations higher than 0.6 mole fraction.

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

PubMed

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.

Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector.

PubMed

Yu, Hai-Ling; Wang, Wen-Yong; Hong, Bo; Zong, Ying; Si, Yan-Ling; Hu, Zhong-Qiang

2016-09-29

Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li + , Na + , K + , Be 2+ , Mg 2+ , Ca 2+ , Co 2+ , Ni 2+ , Cu 2+ ) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

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

NASA Astrophysics Data System (ADS)

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.

The Azocyanide Functional Group.

DTIC Science & Technology

1979-06-05

unsymmetrical dienes; the regioisomer distributions of these unsymmetrical adducts have been correlated with the arylazocyanide ring sub- stituents using Hammet ...the crown ether also acts as a protecting group for the diazonium ion in solution ( equation 1). N NBF4 +[0N-N The efficiency of this protection has...reaction, equation 2) were dramatically slowed in the presence of crown ethers.1 2 However, crown ether solubilization and protection of ArN 2+BF4 hor

Convenient approaches to synthesis of furanoid sugar-aza-crown ethers from C-ribosyl azido aldehyde via a reductive amination/amidation.

PubMed

Hsieh, Yu-Chi; Chir, Jiun-Ly; Zou, Wei; Wu, Hsiu-Han; Wu, An-Tai

2009-05-26

A short and highly efficient route to the alpha-anomer of a furanoid sugar-aza-crown ether was developed by a one-pot reductive amination of an alpha-anomer C-ribosyl azido aldehyde. In addition, the beta-anomer furanoid sugar-aza-crown ether was synthesized from a linear disaccharide precursor via amidation and then followed by microwave-assisted amide reduction.

Jet-cooled electronic and vibrational spectroscopy of crown ethers: benzo-15-crown-5 ether and 4'-amino-benzo-15-crown-5 ether.

PubMed

Shubert, V Alvin; James, William H; Zwier, Timothy S

2009-07-16

Laser-induced fluorescence (LIF), ultraviolet hole-burning (UVHB), and resonant ion-dip infrared (RIDIR) spectroscopies were carried out on isolated benzo-15-crown-5 ether (B15C) and 4'-amino-benzo-15-crown-5 ether (ABC) cooled in a supersonic expansion. Three conformational isomers of B15C and four of ABC were observed and spectroscopically characterized. Full optimizations and harmonic frequency calculations were undertaken for the full set of almost 1700 conformational minima identified in a molecular mechanics force field search. When compared with TDDFT predictions, the S(0)-S(1) origin positions serve as a useful diagnostic of the conformation of the crown ether near the phenyl ring responsible for the UV absorption and to the position of the NH(2) substituent. In-plane orientations for the beta carbons produce red-shifted S(0)-S(1) origins, while out-of-plane "buckling" produces substantial blue shifts of 600 cm(-1) or more. Comparison between the alkyl CH stretch spectra of B15C and ABC divide the spectra into common subgroups shared by the two molecules. The high-frequency CH stretch transitions (above 2930 cm(-1)) reflect the number of CH...O interactions, which in turn track in a general way the degree of buckling of the crown. On this basis, assignments of each of the observed conformational isomers to a class of structure can be made. All the observed structures have some degree of buckling to them, indicating that in the absence of a strong-binding partner, the crown folds in on itself to gain additional stabilization from weak dispersive and CH...O interactions.

A crown ether appended super gelator with multiple stimulus responsiveness.

PubMed

Dong, Shengyi; Zheng, Bo; Xu, Donghua; Yan, Xuzhou; Zhang, Mingming; Huang, Feihe

2012-06-26

A crown ether appended super gelator is designed and synthesized. It can gel a variety of organic solvents and shows excellent gelation properties with both low critical gelation concentration and short gelation time. Due to the introduction of the crown ether moiety and a secondary ammonium unit, the supramolecular gels show reversible gel-sol transitions. The supramolecular gels can also be molded into shape-persistent and free-standing objects. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and pKa determination of new enantiopure dimethyl-substituted acridino-crown ethers containing a carboxyl group: Useful candidates for enantiomeric recognition studies.

PubMed

Németh, Tamás; Dargó, Gergő; Petró, József Levente; Petrik, Zsófia; Lévai, Sándor; Krámos, Balázs; Béni, Zoltán; Nagy, József; Balogh, György Tibor; Huszthy, Péter; Tóth, Tünde

2017-09-01

New enantiopure dimethyl-substituted acridino-18-crown-6 and acridino-21-crown-7 ethers containing a carboxyl group at position 9 of the acridine ring [(S,S)-8, (S,S)-9, (R,R)-10] were synthesized. The pK a values of the new crown ethers [(S,S)-8, (S,S)-9, (R,R)-10] and of an earlier reported macrocycle [(R,R)-2] were determined by UV-pH titrations. Crown ether (S,S)-8 was attached to silica gel by covalent bonds and the enantiomeric separation ability of the newly prepared chiral stationary phase [(S,S)-CSP-12] was studied by high-performance liquid chromatography (HPLC). Homochiral preference was observed and the best separation was achieved for the enantiomers of 1-NEA. Ligands (S,S)-9 and (R,R)-10 are precursors of enantioselective sensor and selector molecules for the enantiomers of protonated primary amines, amino acids, and their derivatives. © 2017 Wiley Periodicals, Inc.

Biomedical potentials of crown ethers: prospective antitumor agents.

PubMed

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.

Novel crown-ether-methylenediphosphonotetrathioate hybrids as Zn(II) chelators.

PubMed

Meltzer, Diana; Gottlieb, Hugo E; Amir, Aviran; Shimon, Linda J W; Fischer, Bilha

2015-12-28

Hybrids of methylenediphosphonotetrathioate and crown-ether (MDPT-CE) were synthesized forming 7-,8-,9-,10- and 13-membered rings. Both 7- and 13-membered ring-containing compounds were found to be highly stable to air-oxidation for at least four weeks. These hybrids bind Zn(II) by both MDPT and CE moieties, forming a 2 : 1 L : Zn(II) complex. Interestingly, the 13-membered ring MDPT-CE showing a high affinity to Zn(II) (Ka 3 ± 0.5 × 10(6) mol(-2) L(2)) does not bind Li(I) or Na(I). The 13-Membered MDPT-CE hybrid is a promising water-soluble, air-stable, high-affinity Zn(II)-chelator, exhibiting selectivity to Zn(II) vs. Mg(II), Na(I), and Li(I).

Vibrational Signatures of Large Amplitude Motions for the Shackled Hydronium Ion Nested in 18-CROWN-6 Ether Using D2 Tagging

NASA Astrophysics Data System (ADS)

Duong, Chinh H.; Menges, Fabian; Craig, Stephanie; Wolke, Conrad T.; Johnson, Mark

2016-06-01

The diffuse spectra arising from the excess proton in dilute acids suggests that its behavior is highly dependent on the local environment surrounding it. In this work, we report how the spectra of the H3O+, NH4+, and CH3NH3+ ions respond when docked to the rigid, tri-coordinated binding pocket of the 18-crown-6 ether using cryogenic ion vibrational predissociation (CIVP) spectroscopy with D2 tagging at 10 K. The H3O+{tiny^bullet}18-crown-6 ether complex displays a broad (350 cm-1 FWHM) unstructured band arising from the OH stretching fundamentals, which is significantly broader than the corresponding band (125 cm-1 FWHM) in the Eigen cation (H9O4+) spectrum. Perdeuterated isotopologue studies for both systems yield sharper bands with clear multiplet structures, indicating that the broadening arises from nuclear quantum effects. The key displacements underlying this coupling were explored using the vibrationally adiabatic scheme introduced by McCoy in the context of similar broadening in the Ca2+OH-(H2O)n system. Christopher J. Johnson, Laura C. Dzugan, Arron B. Wolk, Christopher M. Leavitt, Joseph A. Fournier, Anne B. McCoy, Mark A. Johnson, J. Phys. Chem. A 118, 2014.

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

PubMed

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.

"Crown Ether" Synthesis: An Organic Laboratory Experiment.

ERIC Educational Resources Information Center

Field, Kurt W.; And Others

1979-01-01

This experiment is designed to acquaint the student with a macromolecular synthesis of a crown ether type compound. The starting materials are readily available and the product, a cyclic polyether, belongs to a class of compounds that has aroused the interest of chemist and biologist alike. (Author/BB)

A comparison of complexation of Li+ ion with macrocyclic ligands 15-crown-5 and 12-crown-4 in binary nitromethane-acetonitrile mixtures by using lithium-7 NMR technique and ab initio calculation.

PubMed

Alizadeh, Nina

2011-01-01

Lithium-7 NMR measurements were used to investigate the stoichiometry and stability of Li+ complexes with 15-crown-5 (15C5), benzo-15-crown-5 (B15C5), dibenzo-15-crown-5 (DB15C5) and 12-crown-4 (12C4) in a number of nitromethane (NM)-acetonitrile (AN) binary mixtures. In all cases, the exchange between the free and complexed lithium ion was fast on the NMR time scale and a single population average resonance was observed. While all crown ethers form 1:1 complexes with Li+ ion in the binary mixtures used, both 1:1 and 2:1 (sandwich) complexes were observed between lithium ion and 12C4 in pure nitromethane solution. Stepwise formation constants of the 1:1 and 2:1 (ligand/metal) complexes were evaluated from computer fitting of the NMR-mole ratio data to equations which relate the observed metal ion chemical shifts to formation constants. There is an inverse linear relationship between the logarithms of the stability constants and the mole fraction of acetonitrile in the solvent mixtures. The stability order of the 1:1 complexes was found to be 15C5·Li+>B15C5·Li+>DB15C5·Li+>12C4·Li+. The optimized structures of the free ligands and their 1:1 and 2:1 complexes with Li+ ion were predicted by ab initio theoretical calculations using the Gaussian 98 software, and the results are discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

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

PubMed

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.

Proton-Ionizable Crown Ethers. A Short Review

DTIC Science & Technology

1989-05-30

acid methyl ester using sodium hydride as the base in tetrahydrofuran. The m3thyl ester group was hydrolyzed to the carboxylic acid as shown in Procedure...prepared via the appropriate hydroxydibenzo-crown ether and allyl bromide RýIý R2 or ethyl acrylate as shown in Procedure N. 5 2 . 5 6 Disulfonic acid ...similar to Procedure p. 7 4 Once the precursor binrephtho-crown was obtained, it was coupled with bromoacetic acid methyl ester and R, , - R

On the radiation stability of crown ethers in ionic liquids.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, I.; Marin, T.; Dietz, M.

2011-04-14

Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an ILmore » matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.« less

Studies of flerovium and element 115 homologs with macrocyclic extractants

NASA Astrophysics Data System (ADS)

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 charged metal cations. Extraction chromatography resins produced by Eichrom Technologies, specifically the Pb resin based on di-t-byutlcyclohexano-18-crown-6, were chosen as a starting point for these studies. Simple chemical systems based solely on HCl matrices were explored to determine the extent of extraction for Pb, Sn and Hg on the resin. The kinetics and mechanism of extraction were also explored to determine suitability for a Fl chemical experiment. Systems based on KI/HCl and KI/HNO3 were explored for Bi and Sb. In both cases suitable separations, with high separation factors, were performed with vacuum flow columns containing the Pb-resin. Unfortunately the kinetics of uptake for Hg are far too slow on the traditional crown-ether to perform a Fl experiment and obtain whether or not Fl has true Hg-like character or not. However, the kinetics of Pb and Sn are more than sufficient for a Fl experiment to differentiate between Pb- or Sn-like character. To assess this kinetic issue a novel macrocyclic extractant based on sulfur donors was synthesized. Hexathia-18-crown-6, the sulfur analog of 18-crown-6, was synthesized based with by a template reaction using high dilution techniques. The replacement of oxygen ring atoms with sulfur should give the extractant a softer character, which should allow for far greater affinity toward soft metals such as Hg and Pb. From HCl matrices hexathia-18-crown-6 showed far greater kinetics and affinity for Hg than the Pb-resin; however, no affinity for Pb or Sn was seen. This presumably is due to the fact the charge density of sulfur crown ethers does not point to the center of the ring, and future synthesis of a substituted sulfur crown ether which forces the charge density to mimic that of the traditional crown ether should enable extraction of Pb and Sn to a greater extent than with the Pb-resin. Initial studies show promise for the separation of Bi and Sb from HCl matrices using hexathia-18-crown-6. Other macrocyclic extractants, including 2,2,2-cryptand, calix[6]arene and tetrathia-12-crown-4, were also investigated for comparison to the crown ethers. It was noted that these extractants are inferior compared to the crown and thiacrown ethers for extraction of Fl and element 115 homologs. A potential chemical system for Fl was established based on the Eichrom Pb resin, and insight to an improved system based on thiacrown ethers is presented.

Separation of Long-Lived Fission Products Tc-99 and I-129 from Synthetic Effluents by Crown Ethers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paviet-Hartmann, P.; Hartmann, T.

2006-07-01

To minimize significantly the radio-toxic inventory of nuclear geological repositories to come as well as to reduce the potential of radionuclides migration and to minimize long-term exposure, the concept of partitioning and transmutation (P/T) of nuclear waste is currently discussed. Transmutation offers the possibility to convert radio-toxic radionuclides with long half-lives into radionuclides of shorter half-lives, less toxic isotopes, or even into stable isotopes. Besides the most prominent isotopes of neptunium, plutonium, americium, and curium, the long-lived fission products Tc-99 and I-129 (half-lives of 2.13 x 10{sup 5} years, and 1.57 x 10{sup 7} years, respectively) are promising candidates formore » transmutation in order to prevent their migration from a nuclear repository. Partitioning and transmutation of the most radio-toxic radionuclides will not only minimize the nuclear waste load but most importantly will significantly reduce the long-term radio-toxic hazard of nuclear waste repositories to come. Prior to the deployment of partitioning and transmutation, selective extraction techniques are required to separate the radionuclides of concern. Since the discovery of crown ethers by C. Pedersen, various applications of crown ethers have drawn much attention. Although liquid-liquid extraction of alkali and alkali earth metals by crown ethers has been extensively studied, little data is available on the extraction of Tc-99 and I-129 by crown ethers. The methods developed herein for the specific extraction of Tc-99 and I-129 provide recommendations in support of their selectively extraction from liquid radioactive waste streams, mainly ILW. We report data on the solvent extraction of Tc-99 and I-129 from synthetic effluents by six crown ethers of varying cavity dimensions and derivatization. To satisfy the needs of new extractant systems we are demonstrating that crown ether (CE) based systems have the potential to serve as selective extractants for the separation of these long lived radionuclides from high level nuclear waste (HLW), intermediate level nuclear waste (ILW), and low level nuclear waste (LLW) streams. The experimental results show that dibenzo-18-crown-6 (DB 18C6) is highly selective towards Tc-99, and dicyclohexano-18-crown-6 (DC18C6) is highly selective towards I-129. The nature of the diluent was examined and was shown to be the most influential variable in controlling the extraction coefficients of Tc-99 and I-129. Therefore the addition of polar diluent acetone to non-polar diluent toluene enhanced the distribution coefficient of Tc-99 (DTc) was by a factor of 30. For I-129, the best extraction yield was obtained after introducing tetrachloroethane. Through the process, by a single extraction step, 85 % to 95 % of Tc-99 was extracted from synthetic effluents, while 84 % to 88 % of I-129 was extracted from different acidic media. The extraction by crown ether is a fairly rapid process and the total preparation time of the chemical separation takes about 20 minutes for a batch of eight samples. (authors)« less

Water-soluble polymers and compositions thereof

DOEpatents

Smith, B.F.; Robison, T.W.; Gohdes, J.W.

1999-04-06

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

Water-soluble polymers and compositions thereof

DOEpatents

Smith, Barbara F.; Robison, Thomas W.; Gohdes, Joel W.

2002-01-01

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

Water-soluble polymers and compositions thereof

DOEpatents

Smith, Barbara F.; Robison, Thomas W.; Gohdes, Joel W.

1999-01-01

Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

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

PubMed

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.

Functionalized Derivatives of Benzo-Crown Ethers. Part 4. Antifungal Macrocyclic Supramolecular Complexes of Transition Metal Ions Acting as Lanosterol-14-α-Demethylase Ihibitors

PubMed Central

Barboiu, Mihai; Scozzafava, Andrea; Guran, Cornelia; Diaconescu, Paula; Bojin, Mihaela; Iluc, Vlad; Cot, Louis

1999-01-01

Poly- and mononuclear metal complexes of 2,3,11,12-bis[4-(10-aminodecylcarbonyl)]benzo-18- crown-6 (L) and Cu(II); Ni(II); Co(II) and Cr(III) have been synthesized and characterized by standard physico-chemical procedures. In the newly prepared complexes the crown moiety oxygen atoms of the macrocyclic host did not generally interact with metal ions, whereas the two amino groups of the ligand always did. Several of the newly synthesized compounds act as effective antifungal agents against Aspergillus and Candida spp., some of them showing activities comparable to ketoconazole, with minimum inhibitory concentrations in the range of 0.3−0.5 μg/mL. The mechanism of antifungal action of these coordination compounds is probably connected to an inhibition of lanosterol-14-α-demethylase, a metallo-enzyme playing a key role in sterol biosynthesis in fungi, bacteria and eukariotes. PMID:18475888

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

Increasing the thermopower of crown-ether-bridged anthraquinones.

PubMed

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

2015-11-07

We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either () crown-ether or () 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 and 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 , 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 , 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 (in combination with TTF and Na(+)) and 90 μW m(-1) K(-2) for (with TTF). These are higher or comparable with reported power factors of other organic materials.

Solution behavior of iron(III) and iron(II) porphyrins in DMSO and reaction with superoxide. Effect of neighboring positive charge on thermodynamics, kinetics and nature of iron-(su)peroxo product.

PubMed

Duerr, K; Troeppner, O; Olah, J; Li, J; Zahl, A; Drewello, T; Jux, N; Harvey, J N; Ivanović-Burmazović, I

2012-01-14

The solution behavior of iron(III) and iron(II) complexes of 5(4),10(4),15(4),20(4)-tetra-tert-butyl-5,10,15,20-tetraphenylporphyrin (H(2)tBuTPP) and the reaction with superoxide (KO(2)) in DMSO have been studied in detail. Applying temperature and pressure dependent NMR studies, the thermodynamics of the low-spin/high-spin equilibrium between bis- and mono-DMSO Fe(II) forms have been quantified (K(DMSO) = 0.082 ± 0.002 at 298.2 K, ΔH° = +36 ± 1 kJ mol(-1), ΔS° = +101 ± 4 J K(-1) mol(-1), ΔV° = +16 ± 2 cm(3) mol(-1)). This is a key activation step for substitution and inner-sphere electron transfer. The superoxide binding constant to the iron(II) form of the studied porphyrin complex was found to be (9 ± 0.5) × 10(3) M(-1), and does not change significantly in the presence of the externally added crown ether in DMSO (11 ± 4) × 10(3) M(-1). The rate constants for the superoxide binding (k(on) = (1.30 ± 0.01) × 10(5) M(-1) s(-1)) and release (k(off) = 11.6 ± 0.7 s(-1)) are not affected by the presence of the external crown ether in solution. The resulting iron(II)-superoxide adduct has been characterized (mass spectrometry, EPR, high-pressure UV/Vis spectroscopy) and upon controlled addition of a proton source it regenerates the starting iron(II) complex. Based on DFT calculations, the reaction product without neighboring positive charge has iron(II)-superoxo character in both high-spin side-on and low-spin end-on forms. The results are compared to those obtained for the analogous complex with covalently attached crown ether, and more general conclusions regarding the spin-state equilibrium of iron(II) porphyrins, their reaction with superoxide and the electronic structure of the product species are drawn.

Inhibition of Fibrillar Assemblies of l-Phenylalanine by Crown Ethers: A Potential Approach toward Phenylketonuria.

PubMed

Banik, Debasis; Dutta, Rupam; Banerjee, Pavel; Kundu, Sangita; Sarkar, Nilmoni

2016-08-11

In this article, our aim is to investigate the interaction of l-phenylalanine (l-Phe) fibrils with crown ethers (CEs). For this purpose, two different CEs (15-Crown-5 (15C5) and 18-Crown-6 (18C6)) were used. Interestingly, we have observed that both CEs have the ability to arrest fibril formation. However, 18C6 was found to be a better candidate compared to 15C5. Field emission scanning electron microscopy and fluorescence lifetime imaging microscopy were used to monitor the fibril-arresting kinetics of CEs. The arresting process was further confirmed by fluorescence correlation spectroscopy and nuclear magnetic resonance studies.

Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang

2014-01-01

A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistrymore » calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.« less

Isolation of (CO)1- and (CO2)1- radical complexes of rare earths via Ln(NR2)3/K reduction and [K2(18-crown-6)2]2+ oligomerization.

PubMed

Fang, Ming; Farnaby, Joy H; Ziller, Joseph W; Bates, Jefferson E; Furche, Filipp; Evans, William J

2012-04-11

Deep-blue solutions of Y(2+) formed from Y(NR(2))(3) (R = SiMe(3)) and excess potassium in the presence of 18-crown-6 at -45 °C under vacuum in diethyl ether react with CO at -78 °C to form colorless crystals of the (CO)(1-) radical complex, {[(R(2)N)(3)Y(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 1. The polymeric structure contains trigonal bipyramidal [(R(2)N)(3)Y(μ-CO)(2)](2-) units with axial (CO)(1-) ligands linked by [K(2)(18-crown-6)(2)](2+) dications. Byproducts such as the ynediolate, [(R(2)N)(3)Y](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 2, in which two (CO)(1-) anions are coupled to form (OC≡CO)(2-), and the insertion/rearrangement product, {(R(2)N)(2)Y[OC(═CH(2))Si(Me(2))NSiMe(3)]}[K(18-crown-6)], 3, are common in these reactions that give variable results depending on the specific reaction conditions. The CO reduction in the presence of THF forms a solvated variant of 2, the ynediolate [(R(2)N)(3)Y](2)(μ-OC≡CO)[K(18-crown-6)(THF)(2)](2), 2a. CO(2) reacts analogously with Y(2+) to form the (CO(2))(1-) radical complex, {[(R(2)N)(3)Y(μ-CO(2))(2)][K(2)(18-crown-6)(2)]}(n), 4, that has a structure similar to that of 1. Analogous (CO)(1-) and (OC≡CO)(2-) complexes of lutetium were isolated using Lu(NR(2))(3)/K/18-crown-6: {[(R(2)N)(3)Lu(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 5, [(R(2)N)(3)Lu](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 6, and [(R(2)N)(3)Lu](2)(μ-OC≡CO)[K(18-crown-6)(Et(2)O)(2)](2), 6a. © 2012 American Chemical Society

Stable divalent germanium, tin and lead amino(ether)-phenolate monomeric complexes: structural features, inclusion heterobimetallic complexes, and ROP catalysis.

PubMed

Wang, Lingfang; Roşca, Sorin-Claudiu; Poirier, Valentin; Sinbandhit, Sourisak; Dorcet, Vincent; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann

2014-03-21

Stable germanium(II) and lead(II) amido complexes {LO(i)}M(N(SiMe3)2) (M = Ge(II), Pb(II)) bearing amino(ether)phenolate ligands are readily available using the proteo-ligands {LO(i)}H of general formula 2-CH2NR2-4,6-tBu2-C6H2OH (i = 1, NR2 = N((CH2)2OCH3)2; i = 2, NR2 = NEt2; i = 3, NR2 = aza-15-crown-5) and M(N(SiMe3)2)2 precursors. The molecular structures of these germylenes and plumbylenes, as well as those of {LO(3)}GeCl, {LO(3)}SnCl and of the congeneric {LO(4)}Sn(II)(N(SiMe3)2) where NR2 = aza-12-crown-4, have been determined crystallographically. All complexes are monomeric, with 3-coordinate metal centres. The phenolate systematically acts as a N^O(phenolate) bidentate ligand, with no interactions between the metal and the O(side-arm) atoms in these cases (for {LO(1)}(-), {LO(3)}(-) and {LO(4)}(-)) where they could potentially arise. For each family, the lone pair of electrons essentially features ns(2) character, and there is little, if any, hybridization of the valence orbitals. Heterobimetallic complexes {LO(3)}M(N(SiMe3)2)·LiOTf, where the Li(+) cation sits inside the tethered crown-ether, were prepared by reaction of {LO(3)}M(N(SiMe3)2) and LiOTf (M = Ge(II), Sn(II)). The inclusion of Li(+) (featuring a close contact with the triflate anion) in the macrocycle bears no influence on the coordination sphere of the divalent tetrel element. In association with iPrOH, the amido germylenes, stannylenes and plumbylenes catalyse the controlled polymerisation of L- and racemic lactide. The activity increases linearly according to Ge(II) ≪ Sn(II) ≪ Pb(II). The simple germylenes generate very sluggish catalysts, but the activity is significantly boosted if the heterobimetallic complex {LO(3)}Ge(N(SiMe3)2)·LiOTf is used instead. On the other hand, with 10-25 equiv. of iPrOH, the plumbylenes afford highly active binary catalysts, converting 1000 or 5000 equiv. of monomer at 60 °C within 3 or 45 min, respectively, in a controlled fashion.

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals

NASA Astrophysics Data System (ADS)

Bodnarchuk, Maryna I.; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V.

2015-12-01

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 1011 Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, Brian A.; Taylor, A. Michael

1998-01-01

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene.

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, B.A.; Taylor, A.M.

1998-11-24

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene. 2 figs.

Synthesis, supramolecular behavior, and in vitro photodynamic activities of novel zinc(II) phthalocyanines "side-strapped" with crown ether bridges.

PubMed

Chen, Xing-Wei; Ke, Mei-Rong; Li, Xing-Shu; Lan, Wen-Liang; Zhang, Miao-Fen; Huang, Jian-Dong

2013-12-01

Two new tetra- or di-α-substituted zinc(II) phthalocyanines 5 and 6 have been prepared through a "side-strapped" method. In the molecules, the adjacent benzene rings of the phthalocyanine core are linked at α-position through a triethylene glycol bridge to form a hybrid aza-/oxa-crown ether. The tetra-α-substituted phthalocyanine 5 shows an eclipsed self-assembly property in CH2Cl2 and the effect on the di-α-substituted analogue 6 is significantly weakened. Furthermore, the crown ethers of these compounds can selectively complex with Fe(3+) or Cu(2+) ion in DMF, leading to formation of J-aggregated nano-assemblies, which can be disaggregated in the presence of some organic or inorganic ligands, such as triethylamine, tetramethylethylenediamine, CH3COO(-), or OH(-). In addition, both compounds are efficient singlet oxygen generators with the singlet oxygen quantum yields (Φ(Δ)) of 0.54-0.74 in DMF relative to unsubstituted zinc(II) phthalocyanine (Φ(Δ)=0.56). They exhibit photodynamic activities toward HepG2 human hepatocarcinoma cells, but the compound 6, which has more than 40-fold lower IC50 value (0.08 μM) compared to the analogue 5 (IC50=3.31 μM), shows remarkablely higher in vitro photocytotoxicity due to its significantly higher cellular uptake and singlet oxygen generation efficiency. The results suggest that these compounds can serve as promising multifunctional materials both in (opto)electronic field and photodynamic therapy. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

Trivalent scandium, yttrium and lanthanide complexes with thia-oxa and selena-oxa macrocycles and crown ether coordination.

PubMed

Champion, Martin J D; Farina, Paolo; Levason, William; Reid, Gillian

2013-09-28

Complexes of the oxa-thia macrocycles [18]aneO4S2, [15]aneO3S2 and the oxa-selena macrocycle [18]aneO4Se2 (L) of types [MCl2(L)]FeCl4 (M = Sc or Y) were prepared from [ScCl3(thf)3] or [YCl2(THF)5][YCl4(THF)2] and the ligand in anhydrous MeCN, using FeCl3 as a chloride abstractor. The [MI2(L)]I, [LaI3(L)] and [LuI2(L)]I have been prepared from the ligands and the appropriate anhydrous metal triiodide in MeCN. Complexes of type [LaI3(crown)] and [LuI2(crown)]I (crown = 18-crown-6, 15-crown-5) were made for comparison. Use of the metal iodide results in complexes with high solubility compared to the corresponding chlorides, although also with increased sensitivity to moisture. All complexes were characterised by microanalysis, IR, (1)H, (45)Sc and (77)Se NMR spectroscopy as appropriate. X-ray crystal structures are reported for [ScCl2([18]aneO4S2)][FeCl4], [ScI2([18]aneO4S2)]I, [YCl2(18-crown-6)]3[Y2Cl9], [YCl2([18]aneO4S2)][FeCl4], [LaI3(15-crown-5)], [LaI2(18-crown-6)(MeCN)]I, [LuI(18-crown-6)(MeCN)2]I2, [Lu(15-crown-5)(MeCN)2(OH2)]I3, [LaI3([18]aneO4S2)], [LaI([18]aneO4S2)(OH2)]I2, [LaI3([18]aneO4Se2)] and [LuI2([18]aneO4Se2)]I. In each complex all the neutral donor atoms of the macrocycles are coordinated to the metal centre, showing very rare examples of these oxophilic metal centres coordinated to thioether groups, and the first examples of coordinated selenoether donors. In some cases MeCN or adventitious water displaces halide ligands, but not the S/Se donors from La or Lu complexes. A complex of the oxa-tellura macrocycle [18]aneO4Te2, [ScCl2([18]aneO4Te2)][FeCl4] was isolated, but is unstable in MeCN solution, depositing elemental Te. YCl3 and 18-crown-6 produced [YCl2(18-crown-6)]3[Y2Cl9], the asymmetric unit of which contains two cations with a trans-YCl2 arrangement and a third with a cis-YCl2 group.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1991-02-12

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1990-01-01

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Could LogP be a principal determinant of biological activity in 18-crown-6 ethers? Synthesis of biologically active adamantane-substituted diaza-crowns.

PubMed

Supek, Fran; Ramljak, Tatjana Šumanovac; Marjanović, Marko; Buljubašić, Maja; Kragol, Goran; Ilić, Nataša; Smuc, Tomislav; Zahradka, Davor; Mlinarić-Majerski, Kata; Kralj, Marijeta

2011-08-01

18-crown-6 ethers are known to exert their biological activity by transporting K(+) ions across cell membranes. Using non-linear Support Vector Machines regression, we searched for structural features that influence antiproliferative activity in a diverse set of 19 known oxa-, monoaza- and diaza-18-crown-6 ethers. Here, we show that the logP of the molecule is the most important molecular descriptor, among ∼1300 tested descriptors, in determining biological potency (R(2)(cv) = 0.704). The optimal logP was at 5.5 (Ghose-Crippen ALOGP estimate) while both higher and lower values were detrimental to biological potency. After controlling for logP, we found that the antiproliferative activity of the molecule was generally not affected by side chain length, molecular symmetry, or presence of side chain amide links. To validate this QSAR model, we synthesized six novel, highly lipophilic diaza-18-crown-6 derivatives with adamantane moieties attached to the side arms. These compounds have near-optimal logP values and consequently exhibit strong growth inhibition in various human cancer cell lines and a bacterial system. The bioactivities of different diaza-18-crown-6 analogs in Bacillus subtilis and cancer cells were correlated, suggesting conserved molecular features may be mediating the cytotoxic response. We conclude that relying primarily on the logP is a sensible strategy in preparing future 18-crown-6 analogs with optimized biological activity. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C60.

PubMed

Moreira, Luis; Calbo, Joaquín; Aragó, Juan; Illescas, Beatriz M; Nierengarten, Iwona; Delavaux-Nicot, Béatrice; Ortí, Enrique; Martín, Nazario; Nierengarten, Jean-François

2016-11-30

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH 2 Cl 2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10 8 M -1 . Calculation of the allosteric cooperative factor α for supramolecular complexes [3·1 2 ] and [4·1 2 ] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C 60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C 60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C 60 -C 60 interactions that take place in the more stable syn-disposition of [4·1 2 ].

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals.

PubMed

Bodnarchuk, Maryna I; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V

2015-12-09

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 10(11) Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Host–guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals

PubMed Central

Bodnarchuk, Maryna I.; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V.

2015-01-01

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host–guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 1011 Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs. PMID:26647828

Isolation of Mn(I) Compounds Featuring a Reduced Bis(imino)pyridine Chelate and Their Relevance to Electrocatalytic Hydrogen Production.

PubMed

Mukhopadhyay, Tufan K; MacLean, Nicholas L; Flores, Marco; Groy, Thomas L; Trovitch, Ryan J

2018-05-21

We report the preparation and electronic structure determination of chelate-reduced Mn(I) compounds that are relevant to electrocatalytic proton reduction mediated by [( Ph2PPr PDI)Mn(CO)][Br]. Reducing [( Ph2PPr PDI)Mn(CO)][Br] with excess Na-Hg afforded a neutral paramagnetic complex, ( Ph2PPr PDI)Mn(CO). This compound was found to feature a low spin Mn(I) center and a PDI radical anion as determined by magnetic susceptibility measurement (1.97 μ B ), EPR spectroscopy ( S = 1 / 2 ), and density functional theory calculations. When [( Ph2PPr PDI)Mn(CO)][Br] was reduced with K-Hg, Mn(I) complexes with highly activated CO ligands were obtained. Recrystallization of the reduced product from diethyl ether solution allowed for the isolation of dimeric [(κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 1 ,η 2 -CO)K(Et 2 O)] 2 (ν CO = 1710 cm -1 , 1656 cm -1 ), while methyl tert-butyl ether treatment afforded dimeric [(κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 1 -CO)K(MTBE) 2 ] 2 (ν CO = 1695 cm -1 , MTBE = methyl tert-butyl ether). Addition of 18-crown-6 to these products, or conducting the K-Hg reduction of [( Ph2PPr PDI)Mn(CO)][Br] in the presence of 18-crown-6, allowed for the isolation of a monomeric example, (κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 2 -CO)K(18-crown-6) (ν CO = 1697 cm -1 ). All three complexes were found to be diamagnetic and were characterized thoroughly by multinuclear 1D and 2D NMR spectroscopy and single crystal X-ray diffraction. Detailed analysis of the metrical parameters and spectroscopic properties suggest that all three compounds possess a Mn(I) center that is supported by a PDI dianion. Importantly, (κ 4 - Ph2PPr PDI)Mn(μ-η 1 ,η 2 -CO)K(18-crown-6) was found to react instantaneously with either HBF 4 ·OEt 2 or HOTf to evolve H 2 and generate the corresponding Mn(I) complex, [( Ph2PPr PDI)Mn(CO)][BF 4 ] or [( Ph2PPr PDI)Mn(CO)][OTf], respectively. These products are spectroscopically and electrochemically similar to previously reported [( Ph2PPr PDI)Mn(CO)][Br]. It is believed that the mechanism of [( Ph2PPr PDI)Mn(CO)][Br]-mediated proton reduction involves intermediates that are related to the compounds described herein and that their ambient temperature isolation is aided by the redox active nature of Ph2PPr PDI.

Calix[3]carbazole: A C3-symmetrical receptor for barium ion

NASA Astrophysics Data System (ADS)

Yang, Zhaozheng; Tian, Zhangmin; Yang, Peng; Deng, Tuo; Li, Gang; Zhou, Xue; Chen, Yan; Zhao, Liang; Shen, Hongyan

2017-03-01

The binding ability of calix[3]carbazole (1) to metal ions has been investigated. It is found that 1 could serve as a non crown ether based, C3-symmetrical receptor for Ba2 + via the marriage of cation-π and cation-dipole interactions. FID assay further illustrates that 1 could selectively interact with Ba2 + over Pd2 +. A possible binding mechanism for [1-Ba2 +] complex is proposed.

Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C60 Derivative.

PubMed

Lederer, Marcus; Hahn, Uwe; Strub, Jean-Marc; Cianférani, Sarah; Van Dorsselaer, Alain; Nierengarten, Jean-François; Torres, Tomas; Guldi, Dirk M

2016-02-01

Self-assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18-crown-6 moiety and fullerenes bearing an ammonium head group afforded a novel donor-acceptor hybrid. In reference experiments, fullerenes containing a Boc-protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self-assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×10 5  m -1 have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short-lived charge-separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in-depth electrospray ionization mass spectrometry (ESI-MS) studies, giving rise to the formation and detection of a variety of non-covalently linked species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient removal of caesium ions from aqueous solution using a calix crown ether in ionic liquids: mechanism and radiation effect.

PubMed

Xu, Chao; Yuan, Liyong; Shen, Xinghai; Zhai, Maolin

2010-04-28

The removal of radioactive (137)Cs from nuclear waste is of great importance for both the environment and energy saving. Herein, we report a study on the removal of Cs(+) using a calix crown ether bis(2-propyloxy)calix[4]crown-6 (BPC6) in ionic liquids [C(n)mim][NTf(2)], where [C(n)mim](+) is 1-alkyl-3-methylimidazolium and [NTf(2)](-) is bis(trifluoromethylsulfonyl)imide. The BPC6/[C(n)mim][NTf(2)] system is highly efficient in removing Cs(+) from aqueous solution, even at a low concentration of BPC6. HNO(3) and metal ions such as Na(+), Al(3+) in the aqueous phase interfered with the extraction of Cs(+) by competitive interaction with BPC6 and/or salting-out effect. UV analysis confirmed that the extraction of Cs(+) by the BPC6/[C(n)mim][NTf(2)] system involves a dual extraction mechanism, i.e., via exchange of BPC6.Cs(+) complex or Cs(+) by [C(n)mim](+). Irradiation of [C(4)mim][NTf(2)] dramatically decreases Cs(+) partitioning in the ionic liquid phase by the competitive interaction of radiation-generated H(+) with BPC6, while irradiation of BPC6/[C(4)mim][NTf(2)] decreases Cs(+) partitioning more markedly due to the radiolysis of BPC6.

Ligand reprogramming in dinuclear helicate complexes: a consequence of allosteric or electrostatic effects?

PubMed

Jeffery, John C; Rice, Craig R; Harding, Lindsay P; Baylies, Christian J; Riis-Johannessen, Thomas

2007-01-01

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.

The inverse sandwich complex [(K(18-crown-6))2Cp][CpFe(CO)2]--unpredictable redox reactions of [CpFe(CO)2]I with the silanides Na[SiRtBu2] (R = Me, tBu) and the isoelectronic phosphanyl borohydride K[PtBu2BH3].

PubMed

Sänger, Inge; Kückmann, Theresa I; Dornhaus, Franz; Bolte, Michael; Wagner, Matthias; Lerner, Hans-Wolfram

2012-06-14

The dimeric iron carbonyl [CpFe(CO)(2)](2) and the iodosilanes tBu(2)RSiI were obtained from the reaction of [CpFe(CO)(2)]I with the silanides Na[SiRtBu(2)] (R = Me, tBu) in THF. By the reactions of [CpFe(CO)(2)]I and Na[SiRtBu(2)] (R = Me, tBu) the disilanes tBu(2)RSiSiRtBu(2) (R = Me, tBu) were additionally formed using more than one equivalent of the silanide. In this context it should be noted that reduction of [CpFe(CO)(2)](2) with Na[SitBu(3)] gives the disilanes tBu(3)SiSitBu(3) along with the sodium ferrate [(Na(18-crown-6))(2)Cp][CpFe(CO)(2)]. The potassium analogue [(K(18-crown-6))(2)Cp][CpFe(CO)(2)] (orthorhombic, space group Pmc2(1)), however, could be isolated as a minor product from the reaction of [CpFe(CO)(2)]I with [K(18-crown-6)][PtBu(2)BH(3)]. The reaction of [CpFe(CO)(2)](2) with the potassium benzophenone ketyl radical and subsequent treatment with 18-crown-6 yielded the ferrate [K(18-crown-6)][CpFe(CO)(2)] in THF at room temperature. The crown ether complex [K(18-crown-6)][CpFe(CO)(2)] was analyzed using X-ray crystallography (orthorhombic, space group Pna2(1)) and its thermal behaviour was investigated.

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

PubMed

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.

Lithium Ion Recognition with Nanofluidic Diodes through Host-Guest Complexation in Confined Geometries.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Mafe, Salvador; Niemeyer, Christof M; Ensinger, Wolfgang

2018-05-15

The lithium ion recognition is receiving significant attention because of its application in pharmaceuticals, lubricants and, especially, in energy technology. We present a nanofluidic device for specific lithium ion recognition via host-guest complexation in a confined environment. A lithium-selective receptor molecule, the aminoethyl-benzo-12-crown-4 (BC12C4-NH 2 ), is designed and functionalized on single conical nanopores in polyethylene terephthalate (PET) membranes. The native carboxylic acid groups on the pore walls are covalently linked with the crown ether moieties and the process is monitored from the changes in the current-voltage ( I- V) curves. The B12-crown-4 moieties are known to specifically bind with lithium ions and when the modified pore is exposed to different alkali metal chloride solutions separately, significant changes in the ion current and rectification are only observed for lithium chloride. This fact suggests the generation of positively charged B12C4-Li + complexes on the pore surface. Furthermore, the nanofluidic diode is able to recognize the lithium ion even in the presence of high concentrations of potassium ions in the external electrolyte solution. Thus, this nanodevice suggests a strategy to miniaturize nanofluidic porous systems for efficient recognition, extraction, and separation of lithium from raw materials.

A novel fluorescent probe for Cr3 + based on rhodamine-crown ether conjugate and its application to drinking water examination and bioimaging

NASA Astrophysics Data System (ADS)

Diao, Quanping; Ma, Pinyi; Lv, Linlin; Li, Tiechun; Wang, Xinghua; Song, Daqian

2016-03-01

A trivalent chromium (Cr3 +) fluorescence probe (RhC) was designed and synthesized via Schiff base reaction based on rhodamine-crown ether conjugate. This probe displayed a favorable selectivity for Cr3 + over a range of other common metal ions in DMF/H2O (3:7, v/v; PBS buffer 50 mmol L- 1; pH = 6.8) solution, leading to prominent fluorescence "OFF-ON" switching of the rhodamine fluorophore. The limit of detection was calculated to be 1.5 μmol L- 1 (S/N = 3). The binding ratio of RhC-Cr3 + complex was determined to be 1:2 according to the Job's plot and HR-MS. The probe was successfully applied to examination of Cr3 + in drinking water spiked samples. The average recoveries ranged from 104.9% to 106.9% at spiked concentration level of 10.00 μmol L- 1, and the obtained results were consistent with those obtained using atomic absorption spectrometry (AAS). Moreover, bioimaging experiments showed that RhC can sense the Cr3 + in living cells with a fluorescence enhancement signal.

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

PubMed

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.

12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

NASA Technical Reports Server (NTRS)

Nagasubramanian, G.; Di Stefano, S.

1990-01-01

The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

Characterization of the homologs of flerovium with crown ether based extraction chromatography resins: studies in nitric acid

DOE PAGES

Despotopulos, John D.; Kmak, Kelly N.; Gharibyan, Narek; ...

2016-09-17

Eichrom’s Pb resin, a crown-ether-based extraction chromatography resin, was characterized for separation of the flerovium (Fl) homologs, Pb and Sn. Batch uptake of Pb(II) and Sn(IV) radionuclides was determined from an HNO 3 matrix. Pb(II) was strongly retained on the resin at all HNO 3 concentrations, while Sn(IV) showed no uptake. Extraction kinetics for Pb(II) were examined and show suitable uptake on the second time scale. Here, separation methods for the isolation of individual homologs, Pb(II) and Sn(IV), have been established using 2 mL pre-packed vacuum flow Pb resin columns.

Quantization of bovine serum albumin by fluorescence enhancement effects and corresponding binding of macrocyclic host-protein assembly.

PubMed

Bardhan, Munmun; Misra, Tapas; Ganguly, Tapan

2012-01-05

The present paper reports the investigations on the spectroscopic behavior of the binary complexes of the dye aurintricarboxylic acid (ATA) with protein bovine serum albumin (BSA) and 18-crown 6 (CW) (ATA·BSA, ATA·CW) and the ternary complex ATA·CW·BSA by using UV-vis steady state and time resolved fluorescence spectroscopy. The primary aim of the work is to determine the protein (BSA) quantization by fluorescence enhancement method and investigate the 'enhancer' activity of crown ether (CW) on it to increase the resolution. Steady state and time resolved fluorescence measurements demonstrated how fluorescence intensity of ATA could be used for the determination of the protein BSA in aqueous solution. The binding of dye (probe/fluorescent medicinal molecule) with protein and the denaturing effect in the polar environment of acetonitrile of the dye protein complex act as drug binding as well as drug release activity. Apart from its basic research point of view, the present study also possesses significant importance and applications in the field of medicinal chemistry. Copyright © 2011 Elsevier B.V. All rights reserved.

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

PubMed

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of Cesium Ions with Calix[4]arene-bis(t-octylbenzo-18-crown-6): NMR and Theoretical Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kriz, Jaroslav; Dybal, Jiri; Vanura, Petr

2011-01-01

Using 1H, 13C, and 133Cs NMR spectra, it is shown that calix[4]arene-bis (t-octylbenzo-18-crown-6) (L) forms complexes with one (L 3 Cs ) and two (L 3 2Cs ) Cs ions offered by cesium bis(1,2-dicarbollide) cobaltate (CsDCC) in nitrobenzene-d5. The ions interact with all six oxygen atoms in the crown-ether ring and the electrons of the calixarene aromatic moieties. According to extraction technique, the stability constant of the first complex is log nb(L 3 Cs ) = 8.8 ( 0.1. According to 133Cs NMR spectra, the value of the equilibrium constant of the second complex is log Knb (2)(L 3 2Csmore » ) = 6.3(0.2, i.e., its stabilization constant is log nb(L 3 2Cs ) = 15.1 ( 0.3. Self-diffusion measurements by 1H pulsed-field gradient (PFG) NMRcombined with density functional theory (DFT) calculations suggest that one DCC ion is tightly associated with L 3 Cs , decreasing its positive charge and consequently stabilizing the second complex, L 3 2Cs . Using a saturation-transfer 133Cs NMR technique, the correlation times ex of chemical exchange between L 3 Cs and L 3 2Cs as well as between L 3 2Cs and free Cs ions were determined as 33.6 and 29.2 ms, respectively.« less

A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents

DOE PAGES

Stein, Benjamin W.; Cary, Samantha K.; Berg, John M.; ...

2017-12-06

Here, we report on the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N'-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H 4ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N'-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H 4 tBu 2ChaCha) for the first time. These H 4ChaCha and H 4 tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements.more » As “proof-of-principle,” we isolated the unusual tetrameric cluster [La 2( tBuChaCha) 2] 2 from reactions between H 4 tBu 2ChaCha and La[N(SiMe 3) 2] 3. Characterization of [La 2( tBuChaCha) 2] 2 by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La 3+ and H 4 tBu 2ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.« less

A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stein, Benjamin W.; Cary, Samantha K.; Berg, John M.

Here, we report on the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N'-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H 4ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N'-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H 4 tBu 2ChaCha) for the first time. These H 4ChaCha and H 4 tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements.more » As “proof-of-principle,” we isolated the unusual tetrameric cluster [La 2( tBuChaCha) 2] 2 from reactions between H 4 tBu 2ChaCha and La[N(SiMe 3) 2] 3. Characterization of [La 2( tBuChaCha) 2] 2 by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La 3+ and H 4 tBu 2ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.« less

Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marin, T.; Shkrob, I.; Dietz, M.

2011-04-14

Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between differentmore » clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.« less

A Reliable Hybrid Adsorbent for Efficient Radioactive Cesium Accumulation from Contaminated Wastewater

PubMed Central

Awual, Md. Rabiul; Yaita, Tsuyoshi; Miyazaki, Yuji; Matsumura, Daiju; Shiwaku, Hideaki; Taguchi, Tomitsugu

2016-01-01

Cesium (Cs) removal from nuclear liquid wastewater has become an emerging issue for safeguarding public health after the accident at the Fukushima Daiichi Nuclear Power Plant. A novel macrocyclic ligand of o-benzo-p-xylyl-22-crown-6-ether (OBPX22C6) was developed and successfully immobilized onto mesoporous silica for the preparation of hybrid adsorbent. The benzene ring π electron is the part of crown ether of OBPX22C6 for easy orientation of the macrocyclic compound for making the π electron donation with Cs complexation. The potential and feasibility of the hybrid adsorbent as being Cs selective was evaluated in terms of sensitivity, selectivity and reusability. The results clarified that the Cs removal process was rapid and reached saturation within a short time. Considering the effect of competitive ions, sodium (Na) did not markedly affect the Cs adsorption whereas potassium (K) was slightly affected due to the similar ionic radii. However, the oxygen in long ethylene glycol chain in OBPX22C6 was expected to show strong coordination, including Cs-π interaction with Cs even in the presence of the high amount of K and Na. Due to its high selectivity and reusability, significant volume reduction is expected as this promising hybrid adsorbent is used for Cs removal in Fukushima wastewater. PMID:26818070

A Reliable Hybrid Adsorbent for Efficient Radioactive Cesium Accumulation from Contaminated Wastewater.

PubMed

Awual, Md Rabiul; Yaita, Tsuyoshi; Miyazaki, Yuji; Matsumura, Daiju; Shiwaku, Hideaki; Taguchi, Tomitsugu

2016-01-28

Cesium (Cs) removal from nuclear liquid wastewater has become an emerging issue for safeguarding public health after the accident at the Fukushima Daiichi Nuclear Power Plant. A novel macrocyclic ligand of o-benzo-p-xylyl-22-crown-6-ether (OBPX22C6) was developed and successfully immobilized onto mesoporous silica for the preparation of hybrid adsorbent. The benzene ring π electron is the part of crown ether of OBPX22C6 for easy orientation of the macrocyclic compound for making the π electron donation with Cs complexation. The potential and feasibility of the hybrid adsorbent as being Cs selective was evaluated in terms of sensitivity, selectivity and reusability. The results clarified that the Cs removal process was rapid and reached saturation within a short time. Considering the effect of competitive ions, sodium (Na) did not markedly affect the Cs adsorption whereas potassium (K) was slightly affected due to the similar ionic radii. However, the oxygen in long ethylene glycol chain in OBPX22C6 was expected to show strong coordination, including Cs-π interaction with Cs even in the presence of the high amount of K and Na. Due to its high selectivity and reusability, significant volume reduction is expected as this promising hybrid adsorbent is used for Cs removal in Fukushima wastewater.

A study on 2, 4, 6-trinitrotolurene (TNT) vapor detection by using a quartz crystal microbalance with 18-crown-6 ether film

NASA Astrophysics Data System (ADS)

Phetchakul, Toempong; Phuvanatai, Pavaris

2017-07-01

The application of 18-crown-6 ether film for 2, 4, 6-trinitrotolurene (TNT) vapor detection by using quartz crystal microbalance (QCM) is studied. The film is coated on the quartz electrodes as sensitive material for capture TNT molecule. The parameters that are studied are concentration and mass or thickness of film. When the explosive adheres to surface of the crystal oscillator, the weight is changed and the resonance frequency of the crystal oscillator is shifted lower. The frequency shift (Δf) relates to concentration and mass or thickness. The high concentration and mass/thickness of film enhance the TNT detection.

Polyether complexes of groups 13 and 14.

PubMed

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.

Preparation and Structural Properties of InIII–H Complexes

PubMed Central

Sickerman, Nathaniel S.; Henry, Renée M.; Ziller, Joseph W.

2013-01-01

The use of the tripodal ligands tris[(N'-tert-butylureaylato)-N-ethyl]aminato ([H3buea]3−) and the sulfonamide-based N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzene-sulfonamidato) ([MST]3−) has led to the synthesis of two structurally distinct In(III)–OH complexes. The first example of a five-coordinate indium(III) complex with a terminal hydroxide ligand, K[InIIIH3buea(OH)], was prepared by addition of In(OAc)3 and water to a deprotonated solution of H6buea. X-ray diffraction analysis, as well as FTIR and 1H NMR spectroscopic methods, provided evidence for the formation of a monomeric In(III)–OH complex. The complex contains an intramolecular hydrogen bonding (H-bonding) network involving the In(III)–OH unit and [H3buea]3− ligand, which aided in isolation of the complex. Isotope labeling studies verified the source of the hydroxo ligand as water. Treatment of the [InIIIMST] complex with a mixture of 15-crown-5 ether and NaOH led to isolation of the complex [15-crown-5⊃NaI-(μ-OH)-InIIIMST], whose solid-state structure was confirmed using X-ray diffraction methods. Nuclear magnetic resonance studies on this complex suggest it retains its heterobimetallic structure in solution. PMID:25309019

New polymers for phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1981-01-01

The synthesizing of several polyethylene glycols having crown ethers attached is reported. This work led to the identification of three new polymer types which promise to be more effective at selectively binding specific cell types. Work was completed on identification of chemical properties of the new polymer crowns and on development of new techniques for determination of polymer-phase composition.

Mass dependence of calcium isotope fractionations in crown-ether resin chromatography.

PubMed

Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Tositaka; Sakuma, Yoichi; Suzuki, Tatsuya; Umehara, Saori; Kishimoto, Tadahumi

2010-06-01

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60micro Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of (42)Ca, (43)Ca, (44)Ca, and (48)Ca against (40)Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient epsilon is 3.1x10(-3) for the pair of (40)Ca and (48)Ca. Productivity of enriched (48)Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate.

4-Fluoro-anilinium tetra-chloridoferrate(III) 18-crown-6 clathrate.

PubMed

Ge, Jia-Zhen; Zhao, Min-Min

2010-06-05

The reaction of 4-fluoro-aniline hydro-chloride, 18-crown-6 and ferric chloride in methano-lic solution yields the title compound, (C(6)H(7)FN)[FeCl(4)]·C(12)H(24)O(6), which has an unusual supramolecular structure. N-H⋯O hydrogen-bonding inter-actions between the NH(3) (+) substituents of the 4-fluoro-anilinium cations and the O atoms of the crown ether mol-ecules result in a rotator-stator-like structure.

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

PubMed

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

2014-06-15

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

Octoxy capped Si nanoparticles synthesized by homogeneous reduction of SiCl4 with crown ether alkalide.

PubMed

Sletnes, M; Maria, J; Grande, T; Lindgren, M; Einarsrud, M-A

2014-02-07

Blue-green luminescent octoxy capped Si nanoparticles were synthesized via homogeneous reduction of SiCl4 with the crown ether alkalide K(+)(15-crown-5)2K(-) in tetrahydrofuran. The Si nanoparticles were characterized with respect to size, crystal structure, morphology, surface termination, optical properties and stability. Si diamond structure nanoparticles with narrow size distributions, and average diameters ranging from 3 to 7 nm were obtained. A finite-size effect on the lattice dimensions was observed, in the form of an expansion of the [220] lattice planes of smaller Si nanoparticles. The concentration of SiCl4 was found to be the most important parameter governing the particle size and size distribution. The octoxy capped particles were stable under an ambient atmosphere for at least one month, but exposure to water made them prone to oxidation. An average radiative recombination lifetime of 8.8 ns was measured for the blue-green luminescence. The luminescence appears to originate from surface defects, rather than from quantum confinement.

Alkaline earth cation extraction from acid solution

DOEpatents

Dietz, Mark; Horwitz, E. Philip

2003-01-01

An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

Stereoisomers Separation

NASA Astrophysics Data System (ADS)

Wieczorek, Piotr

The use of capillary electrophoresis for enantiomer separation and optical purity determination is presented. The contents start with basic information about the nature of stereoizomers and the mechanism of enantioseparation using capillary electrophoresis techniques. The molecules to be separated show identical chemical structure and electrochemical behavior. Therefore, the chiral recognition of enantiomers is possible only by bonding to chiral selector and the separation based on very small differences in complexation energies of diastereomer complexes formed. This method is useful for this purpose due to the fact that different compounds can be used as chiral selectors. The mostly used chiral selectors like cyclodextrins, crown ethers, chiral surfactants, macrocyclic antibiotics, transition metal complexes, natural, and synthetic polymers and their application for this purpose is also discussed. Finally, examples of practical applications of electromigration techniques for enantiomers separation and determination are presented.

AFOSR Technical Report Summaries, April-June 1986,

DTIC Science & Technology

1986-06-01

C1HARGE DENSITY. ELECTRODES. INTERrACIAL TENSION. PRESSURE, SIIRFACE PROPERTIES. CORROSION INHIBITION, MOLECULES, ORGANIC COMPOUNDS . SORPTION . FILMS... Perfluorinated derivatives of hydrocarbon Compounds usually ewhibit different propeties than their hydrocarbon analogues. The perfluoro crown ether-s are m.arkedly...Binary Hydrocarbon Mixtures, AD-A166 130 Materials for Emergency Repair AD-A167 094 of Runways. -BROMINE COMPOUNDS AD-Ai64 225 tCHEMICAL LASERS Analysis of

4-Fluoro­anilinium tetra­chloridoferrate(III) 18-crown-6 clathrate

PubMed Central

Ge, Jia-Zhen; Zhao, Min-Min

2010-01-01

The reaction of 4-fluoro­aniline hydro­chloride, 18-crown-6 and ferric chloride in methano­lic solution yields the title compound, (C6H7FN)[FeCl4]·C12H24O6, which has an unusual supramolecular structure. N—H⋯O hydrogen-bonding inter­actions between the NH3 + substituents of the 4-fluoro­anilinium cations and the O atoms of the crown ether mol­ecules result in a rotator–stator-like structure. PMID:21587679

Macrocycles inserted in graphene: from coordination chemistry on graphene to graphitic carbon oxide.

NASA Astrophysics Data System (ADS)

Liu, Wei; Liu, Jingyao; Miao, Maosheng

Tuning the electronic structure and the chemical properties of graphene by binding with metals has become a focus in the area of two dimension materials. Despite many interesting results and promising potentials, the approach suffers from weak binding and the high reactivity of the metal atoms. On the other hand, many macrocyclic molecules such as crown ether show strong and selective binding with metal atoms. The alliance of the two substances will largely benefit the two parallel fields: it will provide a scaffold for coordination chemistry as well as a controllable method for tuning the electronic structure of graphene through strong binding with metals. Here, using crown ether as an example, we demonstrate by first principles calculations that the embedment of macrocyclic molecules into graphene honeycomb lattice can be very thermochemically favored. The embedment of crown ether on graphene can form a family of new two-dimensional materials that possess varying band gaps and band edges. The one with highest O composition (C2O), with similar structure features as graphilic C3N4, shows strong potentials for photolysis and as true two-dimensional superconductor while binding with alkali metals. Calculations are performed on NSF-funded XSEDE resources (TG-DMR130005). This research is also supported by National Natural Science Foundation of China (Grants No. 21373098) in China.

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

PubMed

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.

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

PubMed

Golcs, Ádám; Horváth, Viola; Huszthy, Péter; Tóth, Tünde

2018-05-03

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.

Multistate λ-local-elevation umbrella-sampling (MS-λ-LEUS): method and application to the complexation of cations by crown ethers.

PubMed

Bieler, Noah S; Tschopp, Jan P; Hünenberger, Philippe H

2015-06-09

An extension of the λ-local-elevation umbrella-sampling (λ-LEUS) scheme [ Bieler et al. J. Chem. Theory Comput. 2014 , 10 , 3006 ] is proposed to handle the multistate (MS) situation, i.e. the calculation of the relative free energies of multiple physical states based on a single simulation. The key element of the MS-λ-LEUS approach is to use a single coupling variable Λ controlling successive pairwise mutations between the states of interest in a cyclic fashion. The Λ variable is propagated dynamically as an extended-system variable, using a coordinate transformation with plateaus and a memory-based biasing potential as in λ-LEUS. Compared to other available MS schemes (one-step perturbation, enveloping distribution sampling and conventional λ-dynamics) the proposed method presents a number of important advantages, namely: (i) the physical states are visited explicitly and over finite time periods; (ii) the extent of unphysical space required to ensure transitions is kept minimal and, in particular, one-dimensional; (iii) the setup protocol solely requires the topologies of the physical states; and (iv) the method only requires limited modifications in a simulation code capable of handling two-state mutations. As an initial application, the absolute binding free energies of five alkali cations to three crown ethers in three different solvents are calculated. The results are found to reproduce qualitatively the main experimental trends and, in particular, the experimental selectivity of 18C6 for K(+) in water and methanol, which is interpreted in terms of opposing trends along the cation series between the solvation free energy of the cation and the direct electrostatic interactions within the complex.

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges.

PubMed

Le Derf, Franck; Mazari, Miloud; Mercier, Nicolas; Levillain, Eric; Richomme, Pascal; Becher, Jan; Garín, Javier; Orduna, Jesus; Gorgues, Alain; Sallé, Marc

1999-12-27

A redox responsive ligand incorporating the tetrathiafulvalene unit has been synthesized. The crystal structure of the free ligand (Z)-1 (C(20)H(30)O(5)S(8), triclinic P&onemacr;, Z = 2, a = 9.087(6) Å, b = 11.637(7) Å, c = 14.370(8) Å, alpha = 65.54(3) degrees, beta = 82.32(5) degrees, gamma = 84.18(6) degrees, V = 1368 Å(3)) shows the redox-active tetrathiafulvalene core to be essentially planar, which allows observation of two reversible one-electron processes upon electrochemical oxidation. The efficiency of this system in the control of the reversible complexation/expulsion sequence of a metallic cation (i.e., Ba(2+)) has been made possible thanks to a combination of (a) an unprecedented high coordination ability among tetrathiafulvalene-based macrocycles as determined by LSI mass spectrometry (log K degrees = 3.5, NBA-matrix) as well as by solution investigations ((1)H NMR and cyclic voltammetry titration studies), which remarkably converge to similar binding constant values (i.e., log K degrees = 4.2-4.3), and (b) reversible metal cation expulsion upon electrochemical oxidation to the dicationic state. A channel-like solid-state structure is observed for the Ba(2+) complex (C(20)H(30)O(5)S(8), Ba(2+)(CF(3)SO(3))(2)(2-), (H(2)O)(2), CD(3)CN, monoclinic C2/c, Z = 8, a = 45.66(1) Å, b = 8.897(5) Å, c = 23.124(8) Å, beta = 105.54(4) degrees, V = 9050 Å(3)), which results from the segregated stacking mode of the crown ether and the redox-active tetrathiafulvalene subunits, respectively.

Synthesis, characterization, and sol-gel entrapment of a crown ether-styryl fluoroionophore

PubMed Central

Sui, Zhijie; Hanan, Nathan J.; Phimphivong, Sam; Wysocki, Ronald J.; Saavedra, S. Scott

2011-01-01

The synthesis and initial evaluation of a new dye-functionalized crown-ether, 2-[2-(2,3,5,6,8,9,11,12,14,15-decahydro-1,4,7,10.13.16-benzohexaoxacyclooctadecin)ethenyl]-3-methyl benzothiazolium iodide (denoted BSD), is reported. This molecule contains a benzyl 18-crown-6 moiety as the ionophore and a benzothiazolium to spectrally transduce ion binding. Binding of K+ to BSD in methanol causes shifts in the both absorbance and fluorescence emission maxima, as well as changes in the molar absorptivity and the emission intensity. Apparent dissociation constants (Kd) in the range of 30 – 65 μM were measured. In water and neutral buffer, Kd values were approximately 1 mM. BSD was entrapped in sol-gel films composed of methyltriethoxysilane (MTES) and tetraethylorthosilicate (TEOS) with retention of its spectral properties and minimal leaching. K+ binding to BSD in sol-gels films immersed in pH 7.4 buffer causes significant fluorescence quenching, with an apparent response time of approximately 2 min and an apparent Kd of 1.5 mM. PMID:19253273

Homopolyrotaxanes and Homopolyrotaxane Networks of PEO

NASA Technical Reports Server (NTRS)

Pugh, Coleen; Mattice, Wayne

2005-01-01

In order to identify the optimum size of macrocrown ether for threading, we first investigated the size and shape of simple crown ethers in the melt at 373 K, and their extent of threading with PEO in the melt using coarse-grained Monte Carlo simulations on the 2nnd (second nearest neighbor diamond) lattice, which is a high coordination lattice whose coarse-grained chains can be reverse mapped into fully atomistic models in continuous space.

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

NASA Astrophysics Data System (ADS)

Calisir, Umit; Çiçek, Baki

2017-11-01

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

Nickel Complexes of a Binucleating Ligand Derived from an SCS Pincer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterson, Sonja M.; Helm, Monte L.; Appel, Aaron M.

2015-01-01

A binucleating ligand has been prepared that contains an SCS pincer and three oxygen donor ligands in a partial crown ether loop. To enable metalation with Ni0, a bromoarene precursor was used and resulted in the formation of a nickel-bromide complex in the SCS pincer. Reaction of the nickel complex with a lithium salt yielded a heterobimetallic complex with bromide bridging the two metal centers. The solid-state structures were determined for this heterobimetallic complex and the nickel-bromide precursor, and the two complexes were characterized electrochemically to determine the influence of coordinating the second metal. This research was supported by themore » US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Crystalline smectic E phase revisited in case of symmetrical dibenzo-18-crown-6-ether azomethine dimers

NASA Astrophysics Data System (ADS)

Cozan, Vasile; Ardeleanu, Rodinel; Airinei, Anton; Timpu, Daniel

2018-03-01

Three symmetric azomethine dimers having dibenzo-18-crown-6-ether as internal moiety and halogens (F, Cl, Br) as terminal functional groups were synthesized and characterized by FTIR and 1H NMR spectroscopy. Their thermal behavior was investigated by polarized optical microscopy (POM) and DSC techniques. Interesting textures have been observed at cooling by POM as being representative for a soft crystalline smectic phase. X-ray diffraction measurements in powder at room temperature exhibited a map of reflections corresponding to crystal E phase. The influence of molecular parameters (interdigitation parameter γ, dipole moment, molecular polarizability, halogen radius) on thermal behavior was discussed. The UV-Vis investigations allowed evaluation of photostability and a bathochromic effect was noticed with the increasing of halogen atom radius. Also the values of optical band gap (Eg) are higher than those corresponding to conjugated Schiff bases.

Li+-Permeable Film on Lithium Anode for Lithium Sulfur Battery.

PubMed

Yang, Yan-Bo; Liu, Yun-Xia; Song, Zhiping; Zhou, Yun-Hong; Zhan, Hui

2017-11-08

Lithium-sulfur (Li-S) battery is an important candidate for next-generation energy storage. However, the reaction between polysulfide and lithium (Li) anode brings poor cycling stability, low Coulombic efficiency, and Li corrosion. Herein, we report a Li protection technology. Li metal was treated in crown ether containing electrolyte, and thus, treated Li was further used as the anode in Li-S cell. Due to the coordination between Li + and crown ether, a Li + -permeable film can be formed on Li, and the film is proved to be able to block the detrimental reaction between Li anode and polysulfide. By using the Li anode pretreated in 2 wt % B15C5-containing electrolyte, Li-S cell exhibits significantly improved cycling stability, such as∼900 mAh g -1 after 100 cycles, and high Coulombic efficiency of>93%. In addition, such effect is also notable when high S loading condition is applied.

Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

2001-01-01

A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

Proton Conduction in Tröger's Base Linked Poly(crown ether)s.

PubMed

Patel, Hasmukh A; Selberg, John; Salah, Dhafer; Chen, Haoyuan; Liao, Yijun; Nalluri, Siva Krishna Mohan; Farha, Omar K; Snurr, Randall Q; Rolandi, Marco; Stoddart, J Fraser

2018-06-05

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen, led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host‒guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers - poly(TBL‒DB18C6)-t and poly(TBL‒DB18C6)-c - synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high molecular weight polymers. The macromolecular structures of the isomeric poly(TBL‒DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of free-standing membranes which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of the water as confirmed by water-vapor adsorption isotherms which show a 23 wt% water uptake. The adsorbed water is retained even after reducing the relative humidity to 25 %. The proton conductivity of poly(TBL‒DB18C6)-t which is found to be 1.4 x 10‒4 mS cm‒1 in a humid environment, arises from the hydrogen bonding and the associated proton hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Dual switchable CRET-induced luminescence of CdSe/ZnS quantum dots (QDs) by the hemin/G-quadruplex-bridged aggregation and deaggregation of two-sized QDs.

PubMed

Hu, Lianzhe; Liu, Xiaoqing; Cecconello, Alessandro; Willner, Itamar

2014-10-08

The hemin/G-quadruplex-catalyzed generation of chemiluminescence through the oxidation of luminol by H2O2 stimulates the chemiluminescence resonance energy transfer (CRET) to CdSe/ZnS quantum dots (QDs), resulting in the luminescence of the QDs. By the cyclic K(+)-ion-induced formation of the hemin/G-quadruplex linked to the QDs, and the separation of the G-quadruplex in the presence of 18-crown-6-ether, the ON-OFF switchable CRET-induced luminescence of the QDs is demonstrated. QDs were modified with nucleic acids consisting of the G-quadruplex subunits sequences and of programmed domains that can be cross-linked through hybridization, using an auxiliary scaffold. In the presence of K(+)-ions, the QDs aggregate through the cooperative stabilization of K(+)-ion-stabilized G-quadruplex bridges and duplex domains between the auxiliary scaffold and the nucleic acids associated with the QDs. In the presence of 18-crown-6-ether, the K(+)-ions are eliminated from the G-quadruplex units, leading to the separation of the aggregated QDs. By the cyclic treatment of the QDs with K(+)-ions/18-crown-6-ether, the reversible aggregation/deaggregation of the QDs is demonstrated. The incorporation of hemin into the K(+)-ion-stabilized G-quadruplex leads to the ON-OFF switchable CRET-stimulated luminescence of the QDs. By the mixing of appropriately modified two-sized QDs, emitting at 540 and 610 nm, the dual ON-OFF activation of the luminescence of the QDs is demonstrated.

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2014-07-01

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2013-07-09

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

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

PubMed

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.

Novel benzo-15-crown-5 sol-gel coating for solid-phase microextraction.

PubMed

Wang, Danhua; Xing, Jun; Peng, Jiagang; Wu, Caiying

2003-07-11

A novel dihydroxy-terminated benzo-15-crown-5 was synthesized and applied to prepare a solid-phase microextraction (SPME) fiber coating with sol-gel technology. The optimization of the sol-gel process was studied. The coating method with sol-gel was improved and completed in one run, which economized materials and allowed easier control of the fiber thickness. The repeatability of coating fiber to fiber was better than 4.94% (RSD). The surface of the fiber coating was well-distributed and an electron microscopy experiment suggested a porous structure for crown ether coating, providing high surface areas and allowing for high extraction efficiency. The coating has a high thermal stability (350 degrees C), long lifetime and can stand solvent (organic and inorganic) rinsing due to the chemical binding between the coating and the fiber surface. Non-polar benzene, toluene, ethylbenzene, xylenes, chlorobenzenes, polar phenolic compounds and arylamines were used to evaluate the character of the fiber coating by headspace SPME-gas chromatography technology. For phenols, the linear concentrations ranged from 5 to 1000 microg/l, the detection limits were between 0.05 and 1 microg/l, and the RSD was less than 5%. The addition of benzo-crown ether not only increases the thermal stability of the fiber coating, but also enhances the selectivity of the fiber coating. Compared with commercially available SPME fibers poly(dimethylsiloxane) and polyacrylate, the few phases showed better selectivity and sensitivity towards non-polar and polar aromatic compounds.

NANOSENSOR FOR DETECTION OF SAXITOXIN

EPA Science Inventory

For the past several years, we have been investigating a class of crown ethers having a pendant fluorophore for the detection of saxitoxin (Figure 1).^1-3 We have investigated several aromatic groups for the fluorescence response, including the anthracene,^1,2...

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1980-01-01

Two demonstrations are described: (1) a variant of preparing purple benzene by phase transfer catalysis with quaternary ammonium salts and potassium permanganate in which crown ethers are used; (2) a corridor or "hallway" demonstration in which unknown molecular models are displayed and prizes awarded to students correctly identifying the…

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

PubMed

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.

30 s Response Time of K+ Ion-Selective Hydrogels Functionalized with 18-Crown-6 Ether Based on QCM Sensor.

PubMed

Zhang, Zhenxiao; Dou, Qian; Gao, Hongkai; Bai, Bing; Zhang, Yongmei; Hu, Debo; Yetisen, Ali K; Butt, Haider; Yang, Xiaoxia; Li, Congju; Dai, Qing

2018-03-01

Potassium detection is critical in monitoring imbalances in electrolytes and physiological status. The development of rapid and robust potassium sensors is desirable in clinical chemistry and point-of-care applications. In this study, composite supramolecular hydrogels are investigated: polyethylene glycol methacrylate and acrylamide copolymer (P(PEGMA-co-AM)) are functionalized with 18-crown-6 ether by employing surface initiated polymerization. Real-time potassium ion monitoring is realized by combining these compounds with quartz crystal microbalance. The device demonstrates a rapid response time of ≈30 s and a concentration detection range from 0.5 to 7.0 × 10 -3 m. These hydrogels also exhibit high reusability and K + ion selectivity relative to other cations in biofluids such as Na + , NH 4 + , Mg 2+ , and Ca 2+ . These results provide a new approach for sensing alkali metal ions using P(PEGMA-co-AM) hydrogels. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Mrugalla, Florian; Kast, Stefan M.

2016-09-01

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.

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

PubMed

Mrugalla, Florian; Kast, Stefan M

2016-09-01

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.

Metal-organic and supramolecular architectures based on mechanically interlocked molecules

NASA Astrophysics Data System (ADS)

Fernando, Isurika Rosini

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials. Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, are predicted to be unprecedentedly strong while being lightweight and flexible. With the ultimate goal of achieving control over the functioning of molecular devices in the solid state, a variety of pseudorotaxane building blocks were prepared and characterized, including a novel, rare blue-colored motif. The temperature-dependent assembly/disassembly of pseudorotaxanes was exploited for the construction of single-wavelength colorimetric temperature sensors over a 100 °C window. Pseudorotaxanes based on aromatic crown ether wheels and disubstituted 4,4'-bipyridinium axles were converted into rotaxanes upon binding to metal complexes (zinc, cadmium, mercury, copper, cobalt), and the formation of ordered crystalline arrays was studied in the solid state. The columnar organization of pseudorotaxanes by Hg2X6 2-- complexes (X = Cl, Br, I), leading to unprecedented dichroic (blue/red) rotaxane crystals, was demonstrated for the first time. From the crystal structures studied it became apparent that negatively charged metal complexes are needed for successful assembly with the positively charged pseudorotaxane units. To be able to use the more common, positively charged metal ions for rotaxane framework construction, neutral and negatively charged pseudorotaxanes were synthesized, by attaching anionic substituents (carboxylates, sulfonates) to either the wheel or the axle component. It was found that pseudorotaxane formation also enabled resolution of two sulfonated crown ether isomers, which were inseparable by conventional methods. Organic ligands for MWM precursors were designed and synthesized according to multi-step schemes. Helical metal-complexes based on these ligands were prepared and characterized. Chromatography, Nuclear Magnetic Resonance and UV-Visible spectroscopy, Mass spectrometry, Electrochemistry, Thermogravimetric Analysis and X-ray crystallography were used in identification, purification and characterization of the compounds involved.

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.

PubMed

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.

Developmental toxicity of diphenyl ether herbicides in nestling American kestrels.

PubMed

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.

Conformational effect of dicyclo-hexano-18-crown-6 on isotopic fractionation of zinc: DFT approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boda, A.; Singha Deb, A. K.; Ali, Sk. M.

2014-04-24

Generalized gradient approximated BP86 density functional employing triple zeta valence plus polarization (TZVP) basis set has been used to compute the reduced partition function ratio and isotopic separation factor for zinc isotopes. The isotopic separation factor was found to be in good agreement with the experimental results. The isotopic separation factor was found to depend on the conformation of the crown ether ligand. The trans-trans conformation shows the highest fractionation compared to cis-cis conformer. The present theoretical results can thus be used to plan the isotope separation experiments.

Room temperature rechargeable magnesium batteries with sulfur-containing composite cathodes prepared from elemental sulfur and bis(alkenyl) compound having a cyclic or linear ether unit

NASA Astrophysics Data System (ADS)

Itaoka, Kanae; Kim, In-Tae; Yamabuki, Kazuhiro; Yoshimoto, Nobuko; Tsutsumi, Hiromori

2015-11-01

Room temperature rechargeable magnesium (Mg) batteries are constructed from Mg as a negative material, sulfur (S)-containing composite prepared from elemental sulfur and the bis(alkenyl) compound having a crown ether unit (BUMB18C6) or linear ether unit (UOEE) as a positive material and the simple electrolyte (0.7 mol dm-3 Mg[N(SO2CF3)2]2-triglyme (G3) solution). The reaction between molten S and the bis(alkenyl) compound (BUMB18C6 or UOEE) provides the sulfur-containing composite, S-BUMB18C6 or S-UOEE. Both of the sulfur-containing composites are electrochemically active in the Mg salt-based electrolyte, acetonitrile- or G3- Mg[N(SO2CF3)2]2 electrolyte. The first discharge capacity of the test cells with the sulfur-containing composite is 460 Ah kg-1 (per the weight of sulfur in the composite) with the S-BUMB18C6 electrode and 495 Ah kg-1 with the S-UOEE electrode. According to the continuous charge-discharge cycle tests (at 10th cycle), the discharge capacity of the test cell with the S-BUMB18C6 electrode (68.1 Ah kg-1) is higher than that with the S-UOEE electrode (0.18 Ah kg-1). The crown ether units in the S-BUMB18C6 composite may create ion-conducting paths in the cathode, prevent rise in the internal resistance of the cathode, and provide better cycle performance of the test cells with the S-BUMB18C6 composite electrode than that with the S-UOEE electrode.

UV-Vis Action Spectroscopy Reveals a Conformational Collapse in Hydrogen-Rich Dinucleotide Cation Radicals.

PubMed

Korn, Joseph A; Urban, Jan; Dang, Andy; Nguyen, Huong T H; Tureček, František

2017-09-07

We report the generation of deoxyriboadenosine dinucleotide cation radicals by gas-phase electron transfer to dinucleotide dications and their noncovalent complexes with crown ether ligands. Stable dinucleotide cation radicals of a novel hydrogen-rich type were generated and characterized by tandem mass spectrometry and UV-vis photodissociation (UVPD) action spectroscopy. Electron structure theory analysis indicated that upon electron attachment the dinucleotide dications underwent a conformational collapse followed by intramolecular proton migrations between the nucleobases to give species whose calculated UV-vis absorption spectra matched the UVPD action spectra. Hydrogen-rich cation radicals generated from chimeric riboadenosine 5'-diesters gave UVPD action spectra that pointed to novel zwitterionic structures consisting of aromatic π-electron anion radicals intercalated between stacked positively charged adenine rings. Analogies with DNA ionization are discussed.

Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation.

PubMed

Yamada, Yasuyuki; Kato, Tatsuhisa; Tanaka, Kentaro

2016-08-22

A stacked assembly composed of a porphyrin and two phthalocyanines was prepared through fourfold rotaxane formation. Two phthalocyanine molecules, bearing four 24-crown-8 units, were assembled onto a porphyrin template incorporating four sidechains with two dialkylammonium ions each through pseudorotaxane formation between crown ether units and ammonium ions. The Staudinger phosphite reaction, as the stoppering reaction, resulted in the formation of the stacked heterotrimer composed of a porphyrin and two phthalocyanines connected through a fourfold rotaxane structure. UV/Vis spectroscopic and electrochemical studies of the heterotrimer indicated that there is a significant electronic interaction between the two phthalocyanine units due to the close stacking. The electrochemical oxidation process of the stacked heterotrimer was studied by cyclic voltammetry and spectroelectrochemistry. Electron paramagnetic resonance (EPR) spectroscopy of a dinuclear Cu(II) complex, in which two Cu(II) phthalocyanines were assembled on a metal-free porphyrin template, revealed that two Cu(II) phthalocyanines were located within the stacking distance, which resulted in an antiferromagnetic interaction between the two S=1/2 spins in the ground state of the Cu(2+) ions in the heterotrimer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

Examination and Manipulation of Protein Surface Charge in Solution with Electrospray Ionization Mass Spectrometry

ERIC Educational Resources Information Center

Gross, Deborah S.; Van Ryswyk, Hal

2014-01-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for examining the charge of proteins in solution. The charge can be manipulated through choice of solvent and pH. Furthermore, solution-accessible, protonated lysine side chains can be specifically tagged with 18-crown-6 ether to form noncovalent adducts. Chemical derivatization…

Syntheses, structures, and physicochemical properties of diruthenium compounds of tetrachlorocatecholate with metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) cores (R = CH(3) and C(2)H(5)).

PubMed

Miyasaka, H; Chang, H C; Mochizuki, K; Kitagawa, S

2001-07-02

Metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) (R = CH(3) and CH(3)CH(2)) compounds with tetrachlorocatecholate (Cl(4)Cat) have been synthesized in the corresponding alcohol, MeOH and EtOH, from a nonbridged Ru(2+)-Ru(3+) compound, Na(3)[Ru(2)(Cl(4)Cat)(4)(THF)].3H(2)O.7THF (1). In alcohol solvents, compound 1 is continuously oxidized by oxygen to form Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) species. The presence of a characteristic countercation leads to selective isolation of either Ru(3+)(mu-OR)(2)Ru(3+) or Ru(3.5+)(mu-OR)(2)Ru(3.5+) as a stable adduct species. In methanol, Ph(4)PCl and dibenzo-18-crown-6-ether afford Ru(3+)(mu-OMe)(2)Ru(3+) species, [A](2)[Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] ([A](+) = Ph(4)P(+) (2), [Na(dibenzo-18-crown-6)(H(2)O)(MeOH)](+) (3)), while benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(2)][Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] (4). The air oxidation of 1 in a MeOH/EtOH mixed solvent (1:1 v/v) containing benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(H(2)O)][Ru(2)(Cl(4)Cat)(2)(mu-OMe)(2)Na(2)(EtOH)(2)(H(2)O)(2)(MeOH)(2)].(benzo-15-crown-5) (5). Similarly, the oxidation of 1 in ethanol with Ph(4)PCl provides a Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species, (Ph(4)P)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(6)] (7). A selective formation of a Ru(3+)(mu-OEt)(2)Ru(3+) species, (Ph(4)P)(2)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(2)(H(2)O)(2)] (6), is found in the presence of pyrazine or 2,5-dimethylpyrazine. The crystal structures of these compounds, except 2 and 7, have been determined by X-ray crystallography, and all compounds have been characterized by several spectroscopic and magnetic investigations. The longer Ru-Ru bonds are found in the Ru(3+)(mu-OR)(2)Ru(3+) species (2.606(1) and 2.628(2) A for 3 and 6, respectively) compared with those of Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species (2.5260(6) A and 2.514(2) A for 4 and 5, respectively). These structural features and magnetic and ESR data revealed the electronic configurations of sigma(2)pi(2)delta(2)delta(2)pi(2) and sigma(2)pi(2)delta(2)delta(2)pi(1) for Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+), respectively, in which the former is diamagnetic and the latter is paramagnetic with S = (1)/(2) ground state. Compound 5 forms a one-dimensional chain with alternating arrangement of a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) unit and a free benzo-15-crown-5-ether molecule by intermolecular hydrogen bonds (O(H(2)O).O(crown-ether) = 2.91-3.04 A). The cyclic voltammetry in DMF affords characteristic metal-origin voltammograms; two reversible and two quasi-reversible redox waves were observed. The feature of cyclic voltammograms for the Ru(3+)(mu-OR)(2)Ru(3+) species (2, 3, and 6) and the Ru(3.5+)(mu-OR)(2)Ru(3.5+) species (4 and 7) are similar to each other, indicating that both species are electrochemically stable. The isolation of the pyrazine-trans-coordinated species, [Ph(4)P][Ru(Cl(4)Cat)(2)(L)(2)] (L = pyrazine (8), 2,5-dimethylpyrazine (9)), revealed the selective isolation of 6 from pyrazine-containing solution. UV-vis spectral variation by ethanolysis for 9 demonstrated the selective conversion from the pyrazine-trans-coordinated species to the Ru(3+)(mu-OEt)(2)Ru(3+) species without an oxidation to the Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species. This result suggests the presence of equilibrium between [Ru(Cl(4)Cat)(2)(L)(2)](-) and Ru(3+)(mu-OEt)(2)Ru(3+) species in the synthetic condition for 6.

μ-Hexa-thio-metadiphosphato-bis-[(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)rubidium] aceto-nitrile disolvate.

PubMed

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-12-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto-nitrile solvent mol-ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb(+) ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6](2-) moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6](2-) anion. The hexa-thio-metadiphosphate anion is built up from two tetra-hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto-nitrile solvent mol-ecules stacked along [010].

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.

PubMed

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.

Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

NASA Technical Reports Server (NTRS)

Nagasubramanian, G.; Attia, Alan I.; Halpert, G.

1992-01-01

The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

Synthesis and Characterization of an f-Block Terminal Parent Imido [U=NH] Complex: A Masked Uranium(IV) Nitride

PubMed Central

2014-01-01

Deprotonation of [U(TrenTIPS)(NH2)] (1) [TrenTIPS = N(CH2CH2NSiPri3)3] with organoalkali metal reagents MR (M = Li, R = But; M = Na–Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U(TrenTIPS)(μ-N[H]M)}2] [M = Li–Cs (2a–e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-5 ether (15C5) afforded the uranium terminal parent imido complex [U(TrenTIPS)(NH)][K(15C5)2] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium–imido linkage was found to be essentially linear, and theoretical calculations suggested σ2π4 polarized U–N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(TrenTIPS)(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium–nitride complex [U(TrenTIPS)(N)] (5); this reaction is a new way to prepare the terminal uranium–nitride linkage and was calculated to be exothermic by −3.25 kcal mol–1. PMID:24697157

A method of evaluating crown fuels in forest stands.

Treesearch

Rodney W. Sando; Charles H. Wick

1972-01-01

A method of describing the crown fuels in a forest fuel complex based on crown weight and crown volume was developed. A computer program is an integral part of the method. Crown weight data are presented in graphical form and are separated into hardwood and coniferous fuels. The fuel complex is described using total crown weight per acre, mean height to the base of...

CONVERSION OF DIMETHYL ETHER-BORON TRIFLUORIDE COMPLEX TO POTASSIUM FLUOBORATE

DOEpatents

Eberle, A.R.

1957-06-18

A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate

DOEpatents

Eberle, A.R.

1957-06-18

A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

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

USGS Publications Warehouse

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.

Novel heavy-metal adsorption material: ion-recognition P(NIPAM-co-BCAm) hydrogels for removal of lead(II) ions.

PubMed

Ju, Xiao-Jie; Zhang, Shi-Bo; Zhou, Ming-Yu; Xie, Rui; Yang, Lihua; Chu, Liang-Yin

2009-08-15

A novel polymeric lead(II) adsorbent is prepared by incorporating benzo-18-crown-6-acrylamide (BCAm) as metal ion receptor into the thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) hydrogel. Both stimuli-sensitive properties and the Pb(2+)-adsorption capabilities of the prepared P(NIPAM-co-BCAm) hydrogels are investigated. The prepared P(NIPAM-co-BCAm) hydrogels exhibit good ion-recognition and Pb(2+)-adsorption characteristics. When crown ether units capture Pb(2+) and form BCAm/Pb(2+) host-guest complexes, the lower critical solution temperature (LCST) of the hydrogel shifts to a higher temperature due to both the repulsion among charged BCAm/Pb(2+) groups and the osmotic pressure within the hydrogel. The adsorption results at different temperatures show that P(NIPAM-co-BCAm) hydrogels adsorb Pb(2+) ions at temperature lower than the LCST, but undergo desorption at temperature higher than the LCST due to the "stretch-to-shrink" configuration change of copolymer networks which is triggered by the change in environmental temperature. This kind of ion-recognition hydrogel is promising as a novel adsorption material for adsorption and separation of Pb(2+) ions. The adsorption and desorption of Pb(2+) could be rationally achieved by simply changing the environmental temperature.

Combined transuranic-strontium extraction process

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1992-12-08

The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal. 3 figs.

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

DTIC Science & Technology

1987-06-01

38.) of slightly bluish green powder (Anal, see Table I). tH NMR(CDCl 3 ) 8.02(8H,s), 4.7-3.6(64H,m), - 3.41(2H,s). ZnCRPc was obtained by reaction of...J.P.; Bencosme, S.; Evitt, E., Sessler, J. Chem. Phys. 1984, 86, 161. Mialoco, C.; Giannotti, A., Maillard , P.; Momeuteau, M. Chem. Phys. Lett. 1984

Combined transuranic-strontium extraction process

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1992-01-01

The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal.

μ-Hexa­thio­metadiphosphato-bis­[(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-κ6 O)rubidium] aceto­nitrile disolvate

PubMed Central

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-01-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto­nitrile solvent mol­ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb+ ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6]2− moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6]2− anion. The hexa­thio­metadiphosphate anion is built up from two tetra­hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto­nitrile solvent mol­ecules stacked along [010]. PMID:24860286

Molecular recognition of organic ammonium ions in solution using synthetic receptors

PubMed Central

Späth, Andreas

2010-01-01

Summary Ammonium ions are ubiquitous in chemistry and molecular biology. Considerable efforts have been undertaken to develop synthetic receptors for their selective molecular recognition. The type of host compounds for organic ammonium ion binding span a wide range from crown ethers to calixarenes to metal complexes. Typical intermolecular interactions are hydrogen bonds, electrostatic and cation–π interactions, hydrophobic interactions or reversible covalent bond formation. In this review we discuss the different classes of synthetic receptors for organic ammonium ion recognition and illustrate the scope and limitations of each class with selected examples from the recent literature. The molecular recognition of ammonium ions in amino acids is included and the enantioselective binding of chiral ammonium ions by synthetic receptors is also covered. In our conclusion we compare the strengths and weaknesses of the different types of ammonium ion receptors which may help to select the best approach for specific applications. PMID:20502608

Developmental toxicity of diphenyl ether herbicides in birds

USGS Publications Warehouse

Hoffman, D.J.; Rattner, B.A.; Bunck, C.M.

1991-01-01

Diphenyl ether herblcldes, includlng nitrofen, have been identified as mammalian teratogens and cause perinatal mortality. American kestrel (Falco sparverius) nestlings were orally dosed for 10 days w1th 5 ul/g of corn oil (controls) or one of the diphenyl ether herbicides (nitrofen, bifenox, or oxyfluorofen). At 500 mg/kg, nitrofen resulted in complete mortality, bifenox in high (66%) mortality, and oxyfluorofen in no mortality. Nitrofen, at 250 mg/kg, reduced nestling growth, as reflected by decreased body weight and bone length. Bifenox at 250 mg/kg had less effect on growth than nitrofen but crown rump, humerus, radiusulna and femur lengths were significantly less than controls. Liver welght (percent of body welght) increased with 50 mg/kg nitrofen. Other manifestations of hepatotoxicity following nitrofen ingestion included increased hepatic GSH peroxidase activity with 0 mg/kg nitrofen, and increased plasma enzyme activities for ALT, AST. and LDHL with 250 mg/kg. Blfenox lngestion (50 mg/kg) resulted in increased hepatlc GSH peroxidase activity. Nitrofen exposure increased total plasma thyroxlne (T4) concentratlon. These findings suggest that altricial nestllng kestrels are more sensitive to diphenyl ether herbicides than precocial young or adult birds.

Extractant composition including crown ether and calixarene extractants

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

2009-04-28

An extractant composition comprising a mixed extractant solvent consisting of calix[4] arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present at from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.

Liquid chromatographic extraction medium

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1994-01-01

A method and apparatus for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column is described. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water.

High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

NASA Astrophysics Data System (ADS)

Liu, Xiaodong; Lei, Ming; Zhou, Yi; Song, Bo; Li, Yongfang

2015-08-01

Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH3NH3PbI3-XClX. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (Jsc). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.

High-throughput and selective solid-phase extraction of urinary catecholamines by crown ether-modified resin composite fiber.

PubMed

Chen, LiQin; Wang, Hui; Xu, Zhen; Zhang, QiuYue; Liu, Jia; Shen, Jun; Zhang, WanQi

2018-08-03

In the present study, we developed a simple and high-throughput solid phase extraction (SPE) procedure for selective extraction of catecholamines (CAs) in urine samples. The SPE adsorbents were electrospun composite fibers functionalized with 4-carboxybenzo-18-crown-6 ether modified XAD resin and polystyrene, which were packed into 96-well columns and used for high-throughput selective extraction of CAs in healthy human urine samples. Moreover, the extraction efficiency of packed-fiber SPE (PFSPE) was examined by high performance liquid chromatography coupled with fluorescence detector. The parameters affecting the extraction efficiency and impurity removal efficiency were optimized, and good linearity ranging from 0.5 to 400 ng/mL was obtained with a low limit of detection (LOD, 0.2-0.5 ng/mL) and a good repeatability (2.7%-3.7%, n = 6). The extraction recoveries of three CAs ranged from 70.5% to 119.5%. Furthermore, stable and reliable results obtained by the fluorescence detector were superior to those obtained by the electrochemical detector. Collectively, PFSPE coupled with 96-well columns was a simple, rapid, selective, high-throughput and cost-efficient method, and the proposed method could be applied in clinical chemistry. Copyright © 2018 Elsevier B.V. All rights reserved.

Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Kuz'mina, K. I.; Lan, Pham Thi; Kuz'mina, I. A.; Sharnin, V. A.

2014-08-01

The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χDMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δtr G ○(3Gly), possibly indicating the formation of more stable 3Gly-H2O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation's contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H2O-DMSO solvents is analyzed, and the key role of 3Gly solvation's contribution to the change in the stability of [3Gly18C6] upon moving from H2O to mixtures with DMSO is revealed.

Highly K+ -Selective Fluorescent Probes for Lifetime Sensing of K+ in Living Cells.

PubMed

Schwarze, Thomas; Mertens, Monique; Müller, Peter; Riemer, Janine; Wessig, Pablo; Holdt, Hans-Jürgen

2017-12-06

The new K + -selective fluorescent probes 1 and 2 were obtained by Cu I -catalyzed 1,3-dipolar azide alkyne cycloaddition (CuAAC) reactions of an alkyne-substituted [1,3]dioxolo[4,5-f][1,3]benzodioxole (DBD) ester fluorophore with azido-functionalized N-phenylaza-18-crown-6 ether and N-(o-isopropoxy) phenylaza-18-crown-6 ether, respectively. Probes 1 and 2 allow the detection of K + in the presence of Na + in water by fluorescence enhancement (2.2 for 1 at 2000 mm K + and 2.5 for 2 at 160 mm K + ). Fluorescence lifetime measurements in the absence and presence of K + revealed bi-exponential decay kinetics with similar lifetimes, however with different proportions changing the averaged fluorescence decay times (τ f(av) ). For 1 a decrease of τ f(av) from 12.4 to 9.3 ns and for 2 an increase from 17.8 to 21.8 ns was observed. Variation of the substituent in ortho position of the aniline unit of the N-phenylaza-18-crown-6 host permits the modulation of the K d value for a certain K + concentration. For example, substitution of H in 1 by the isopropoxy group (2) decreased the K d value from >300 mm to 10 mm. 2 was chosen for studying the efflux of K + from human red blood cells (RBC). Upon addition of the Ca 2+ ionophor ionomycin to a RBC suspension in a buffer containing Ca 2+ , the fluorescence of 2 slightly rose within 10 min, however, after 120 min a significant increase was observed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

DOEpatents

Liepins, R.; Aldissi, M.

1984-07-27

Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

DOEpatents

Liepins, Raimond; Aldissi, Mahmoud

1988-01-01

Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

The Crown Ether Promoted Base Degradation of p-Carborane.

DTIC Science & Technology

1982-04-20

soluble in methylene chloride, benzene, ethanol and tetrahydrofuran. The cation may be exchanged by a two-phase acidification procedure in which the [K...472 Attn: CRD-AA-IP 800 North Quincy Street P.O. Box 1211 Arlington, Virginia 22217 2 Research Triangle Park, N.C. 27709 ONR Branch Office Naval Ocean ...21401 Washington, D.C. 20360 1 Naval Ocean Systems Center Defense Documentation Center Attn: Dr. S. Yamamoto, Marine Building 5, Cameron Station Sciences

Liquid chromatographic extraction medium

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1994-09-13

A method and apparatus are disclosed for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water. 1 fig.

Catalytic Activity of Thiolate-Bridged Diruthenium Complexes Bearing Pendent Ether Moieties in the Oxidation of Molecular Dihydrogen.

PubMed

Yuki, Masahiro; Sakata, Ken; Kikuchi, Shoma; Kawai, Hiroyuki; Takahashi, Tsuyoshi; Ando, Masaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

2017-01-23

Thiolate-bridged diruthenium complexes bearing pendent ethers have been found to work as effective catalysts toward the oxidation of molecular dihydrogen into protons and electrons in water. The pendent ether moiety in the complex plays an important role to facilitate the proton transfer between the metal center and the external proton acceptor. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for liquid chromatographic extraction of strontium from acid solutions

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1992-01-01

A method and apparatus for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column is described. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water.

Reactions and Interactions in Liquid Crystalline Media

DTIC Science & Technology

1991-10-30

nematic lyophases of potassium laurate, myristyl tri methylammonium bromide or sodium decylsulfate with 1-decanol and 23 water. A strong retardation of the...crystalline polyacrylate crosslinked elastomers were synthesized. 198c 0 0 96 0 0 0O-(CH12 ) 2 -0O(k 97 Crosslinking, up to 10% of structural units produced...in their isotropic state and they work as the transporting phase for the azo-crown ether molecules. The permeation of K+ from a potassium p

High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiaodong; Zhou, Yi, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn; Song, Bo, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn

2015-08-10

Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH{sub 3}NH{sub 3}PbI{sub 3−X}Cl{sub X}. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than thatmore » of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (J{sub sc}). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.« less

Crystallization process of zeolite rho prepared by hydrothermal synthesis using 18-crown-6 ether as organic template.

PubMed

Araki, Sadao; Kiyohara, Yasato; Tanaka, Shunsuke; Miyake, Yoshikazu

2012-06-15

There are many viewpoints on the formation mechanisms for zeolites, but the details are not clear. An understanding of the elementary steps for their formation is important for the development of large-scale membranes and efficient manufacturing processes. In this study, the effects of silicon, aluminum, and the incorporation of 18-crown-6 (18C6) ether, on the formation of zeolite rho, using 18C6 as the structure directing agent (SDA) have been investigated by using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray fluorescence spectrometry (EDX), nuclear magnetic resonance spectroscopy (NMR), thermo gravimetric analysis (TGA), and the pH measurement. These results suggested that a zeolite rho has four synthesis steps; (1) 0-3 h, the dehydration and condensation reaction between the silica and alumina to form amorphous aluminosilicates; (2) 3-20 h, the particle growth and aggregation process for the amorphous aluminosilicates; (3) 20-48 h, the crystallization and crystal growth of zeolite rho, with the incorporation of 18C6; and (4) 48-96 h, gentle growth with an increase in Na/Si ratio and a change in rate for the bounding state between the silica- and the alumina-based species. We consider the above to reflect the four steps for the formation of zeolite rho. Copyright © 2012 Elsevier Inc. All rights reserved.

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

PubMed

Liebing, Phil; Zaeni, Ahmad; Olbrich, Falk; Edelmann, Frank T

2016-12-01

The crystal and mol-ecular strutures of two solvated forms of [K(18 c 6)]OAc (18 c 6 = 18-crown-6 = 1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane and OAc = acetate) were determined by single-crystal X-ray diffraction, namely (acetato-κ 2 O , O ')(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ 6 O )potassium dihydrate, [K(CH 3 COO)(C 12 H 24 O 6 )]·2H 2 O ( 1 ) and (acetato-κ 2 O , O ')aqua-(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ 6 O )potassium acetic acid monosolvate [K(CH 3 COO)(C 12 H 24 O 6 )(H 2 O)]·CH 3 COOH ( 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 O 6 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.

Luminescence, electrochemistry and host-guest properties of dinuclear platinum(ii) terpyridyl complexes of sulfur-containing bridging ligands.

PubMed

Tang, Rowena Pui-Ling; Wong, Keith Man-Chung; Zhu, Nianyong; Yam, Vivian Wing-Wah

2009-05-28

A series of dinuclear platinum(ii) terpyridyl and terpyridyl-crown complexes with 2,2-dicyano-1,1-ethylenedithiolate (i-mnt), 1,3-benzenedithiolate (SC(6)H(4)S-1,3) and N,N-diethyldithiocarbamate (dtc) bridging ligands have been synthesized and characterized. Their photophysical and electrochemical properties, together with that of the related mononuclear platinum(ii) terpyridyl-crown complex and its crown-free analogue, have been studied. The ion-binding properties of the terpyridyl-crown complexes have been determined by electronic absorption spectroscopy and ESI-mass spectrometry. The X-ray crystal structures of [Pt(trpyC[triple bond, length as m-dash]C-benzo-15-crown-5)Cl]PF(6), [{Pt(trpy)}(2)(micro-SC(6)H(4)S-1,3)](PF(6))(2) and [{Pt(trpy)}(2){micro-(i-mnt)}](PF(6))(2) have also been determined.

A new high-speed hollow fiber based liquid phase microextraction method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography.

PubMed

Sarafraz-Yazdi, A; Mofazzeli, F; Es'haghi, Z

2009-07-15

A new and fast hollow fiber based liquid phase microextraction (HF-LPME) method using volatile organic solvents coupled with high-performance liquid chromatography (HPLC) was developed for determination of aromatic amines in the environmental water samples. Analytes including 3-nitroaniline, 3-chloroaniline and 4-bromoaniline were extracted from 6 mL basic aqueous sample solution (donor phase, NaOH 1 mol L(-1)) into the thin film of organic solvent that surrounded and impregnated the pores of the polypropylene hollow fiber wall (toluene, 20 microL), then back-extracted into the 6 mL acidified aqueous solution (acceptor phase, HCl 0.5 mol L(-1)) in the lumen of the two-end sealed hollow fiber. After the extraction, 5 microL of the acceptor phase was withdrawn into the syringe and injected directly into the HPLC system for the analysis. The parameters influencing the extraction efficiency including the kind of organic solvent and its volume, composition of donor and acceptor phases and the volume ratio between them, extraction time, stirring rate, salt addition and the effect of the analyte complexation with 18-crown-6 ether were investigated and optimized. Under the optimal conditions (donor phase: 6 mL of 1 mol L(-1) NaOH with 10% NaCl; organic phase: 20 microL of toluene; acceptor phase: 6 microL of 0.5 mol L(-1) HCl and 600 mmol L(-1) 18-crown-6 ether; pre-extraction and back-extraction times: 75 s and 10 min, respectively; stirring rate: 800 rpm), the obtained EFs were between 259 and 674, dynamic linear ranges were 0.1-1000 microg L(-1) (R>0.9991), and also the limits of detection were in the range of 0.01-0.1 micro gL(-1). The proposed procedure worked very well for real environmental water samples with microgram per liter level of the analytes, and good relative recoveries (91-102%) were obtained for the spiked sample solutions.

Remote camera monitoring and a mark – recapture study of the wandering salamander in a redwood forest canopy

Treesearch

Jim Campbell-Spickler; Stephen C. Sillett

2017-01-01

Crowns of old redwoods (Sequoia sempervirens (D. Don) Endl.) are teaming with life. Storm damage followed by recovery via trunk reiteration increases the structural complexity of redwood crowns over time. Bark and wood surfaces within complex redwood crowns accumulate debris and become covered with epiphytes. Arboreal soils develop beneath...

Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Despotopulos, John D.

2015-03-12

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

Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies.

PubMed

Franco, Delphine; Wenger, Karine; Antonczak, Serge; Cabrol-Bass, Daniel; Duñach, Elisabet; Rocamora, Mercè; Gomez, Montserrat; Muller, Guillermo

2002-02-02

The intramolecular transfer of the allyl group of functionalized allyl aryl ethers to an aldehyde group in the presence of Ni0 complexes was studied from chemical, electrochemical and theoretical points of view. The chemical reaction involves the addition of Ni0 to the allyl ether followed by stoichiometric allylation. The electrochemical process is catalytic in nickel and involves the reduction of intermediate eta3-allylnickel(II) complexes.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 {sup 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 {sup 90}Sr;more » 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{prime}(5{prime})[(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.« less

Revisiting the Formation and Tunable Dissociation of a [2]Pseudorotaxane Formed by Slippage Approach

PubMed Central

Leung, Ken Cham-Fai; Lau, Kwun-Ngai; Wong, Wing-Yan

2015-01-01

A new [2]pseudorotaxane DB24C8⊃1-H·PF6 with dibenzo[24]crown-8 (DB24C8) crown ether-dibenzylammonium (1-H·PF6) binding which was formed by slippage approach at different solvents and temperature, had been isolated and characterized by NMR spectroscopy and mass spectrometry. The [2]pseudorotaxane DB24C8⊃1-H·PF6 was stable at room temperature. The dissociation rate of [2]pseudorotaxane DB24C8⊃1-H·PF6 could be tuned by using different stimuli such as triethylamine (TEA)/diisopropylethylamine (DIPEA) and dimethyl sulfoxide (DMSO). In particular, the dissociation of [2]pseudorotaxane DB24C8⊃1-H·PF6 by an excess of TEA/DIPEA base mixture possessed a long and sustained, complete dissociation over 60 days. Other stimuli by DMSO possessed a relatively fast dissociation over 24 h. PMID:25872145

Dibenzo-18-crown-6–picric acid–water (1/2/3)

PubMed Central

Saleh, Muhammad Idiris; Kusrini, Eny; Rosli, Mohd Mustaqim; Fun, Hoong-Kun

2008-01-01

In the crown ether ring of the title compound, C20H24O6·2C6H3N3O7·3H2O, the O—C(H2)—C(H2)—O torsion angles indicate a gauche conformation of the ethyl­eneoxy units, while the C—O—C—C torsion angles indicate planarity of these segments; the dihedral angle between the two benzene rings is 44.53 (13)°. In both picric acid mol­ecules, one of the nitro groups is twisted away from the attached ring. The mol­ecules are linked into chains along the b axis via inter­molecular O—H⋯O hydrogen bonds. In addition, the crystal structure is stabilized by C—H⋯O hydrogen bonds and π–π inter­actions [centroid–centroid distance between benzene rings = 3.5697 (16) Å]. PMID:21202944

Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food.

PubMed

Yu, Jianxin; Wu, Caiying; Xing, Jun

2004-05-21

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.

Conductivities of the ionic complexes of two cyclic polyethers

NASA Technical Reports Server (NTRS)

Fielder, W. L.; Odonnell, P. M.

1975-01-01

The conductivities of the solid potassium thiocyanate complex of both dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 were measured at 300K (27 C). Saturated aqueous potassium thiocyanate and graphite were used as ion-transporting and ion-blocking electrodes, respectively. The ionic conductivity predominated for both samples, but it was many orders of magnitude smaller than the value previously reported. The ionic conductivity of the dicyclohexyl complex (the better conductor) was 0.000003 ohm/cm. Crown complexes, in general, do not appear promising as potassium ion solid electrolytes contrary to claims in the patent literature.

Biomechanical validation of an artificial tooth–periodontal ligament–bone complex for in vitro orthodontic load measurement

PubMed Central

Xia, Zeyang; Chen, Jie

2014-01-01

Objectives To develop an artificial tooth–periodontal ligament (PDL)–bone complex (ATPBC) that simulates clinical crown displacement. Material and Methods An ATPBC was created. It had a socket hosting a tooth with a thin layer of silicon mixture in between for simulating the PDL. The complex was attached to a device that allows applying a controlled force to the crown and measuring the resulting crown displacement. Crown displacements were compared to previously published data for validation. Results The ATPBC that had a PDL made of two types of silicones, 50% gasket sealant No. 2 and 50% RTV 587 silicone, with a thickness of 0.3 mm, simulated the PDL well. The mechanical behaviors (1) force-displacement relationship, (2) stress relaxation, (3) creep, and (4) hysteresis were validated by the published results. Conclusion The ATPBC simulated the crown displacement behavior reported from biological studies well. PMID:22970752

Broadband Microwave Spectroscopy as a Tool to Study Intermolecular Interactions in the Diphenyl Ether - Water System

NASA Astrophysics Data System (ADS)

Fatima, Mariyam; Perez, Cristobal; Schnell, Melanie

2017-06-01

Many biological processes, such as chemical recognition and protein folding, are mainly controlled by the interplay of hydrogen bonds and dispersive forces. This interplay also occurs between organic molecules and solvent water molecules. Broadband rotational spectroscopy studies of weakly bound complexes are able to accurately reveal the structures and internal dynamics of molecular clusters isolated in the gas phase. Amongst them, water clusters with organic molecules are of particular interest. In this work, we investigate the interplay between different types of weak intermolecular interactions and how it controls the preferred interaction sites of aromatic ethers, where dispersive interactions may play a significant role. We present our results on diphenyl ether (C_{12}H_{10}O, 1,1'-Oxydibenzene) complexed with up to three molecules of water. Diphenyl ether is a flexible molecule, and it offers two competing binding sites for water: the ether oxygen and the aromatic π system. In order to determine the structure of the diphenyl ether-water complexes, we targeted transitions in the 2-8 GHz range using broadband rotational spectroscopy. We identify two isomers with one water, one with two water, and one with three water molecules. Further analysis from isotopic substitution measurements provided accurate structural information. The preferred interactions, as well as the observed structural changes induced upon complexation, will be presented and discussed.

Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

2007-11-06

A mixed extractant solvent including calix[4]arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

Sorbents based on asbestos with a layer of an hydroxyethylcyclam derivative of PVC containing aquacomplexes of sulfuric acid or sodium hydroxide with aza-crown groups

NASA Astrophysics Data System (ADS)

Tsivadze, A. Yu.; Fridman, A. Ya.; Morozova, E. M.; Sokolova, N. P.; Voloshchuk, A. M.; Petukhova, G. A.; Bardyshev, I. I.; Gorbunov, A. M.; Polyakova, I. Ya.; Titova, V. N.; Yavich, A. A.; Novikov, A. K.; Petrova, N. V.

2016-07-01

Aquacomplexes of sulfuric acid and sodium hydroxide with aza-crown groups are synthesized in cavities of a sorbent from the porous layer of a PVC cyclam-derivative grafted onto fibers of asbestos fabric. The structure of sorbents with complexes is studied and their adsorption characteristics are determined. It is shown that the affinity of the developed surface toward ethanol, benzene, and hexane depends on the nature of complexes in the pore walls, and the volume of cavities formed as a result of the pores on the developed asbestos surface being coated with networks of aza-crown groups is larger than that of cavities with walls of aza-crown groups in the layers of a PVC cyclam derivative. Indicators of H+- and OH--conductivity of sorbents with complexes as electrochemical bridges are determined. It is shown that the major part of H+- and OH--ions moves through complexes with aza-crown groups in the region of cavities formed of pores on the surface of asbestos.

RECOVERY OF URANIUM FROM PITCHBLENDE

DOEpatents

Ruehle, A.E.

1958-06-24

The decontamination of uranium from molybdenum is described. When acid solutions containing uranyl nitrate are contacted with ether for the purpose of extracting the uranium values, complex molybdenum compounds are coextracted with the uranium and also again back-extracted from the ether with the uranium. This invention provides a process for extracting uranium in which coextraction of molybdenum is avoided. It has been found that polyhydric alcohols form complexes with molybdenum which are preferentially water-soluble are taken up by the ether extractant to only a very minor degree. The preferred embodiment of the process uses mannitol, sorbitol or a mixture of the two as the complexing agent.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Despotopulos, John D.; Kmak, Kelly N.; Gharibyan, Narek

Eichrom’s Pb resin, a crown-ether-based extraction chromatography resin, was characterized for separation of the flerovium (Fl) homologs, Pb and Sn. Batch uptake of Pb(II) and Sn(IV) radionuclides was determined from an HNO 3 matrix. Pb(II) was strongly retained on the resin at all HNO 3 concentrations, while Sn(IV) showed no uptake. Extraction kinetics for Pb(II) were examined and show suitable uptake on the second time scale. Here, separation methods for the isolation of individual homologs, Pb(II) and Sn(IV), have been established using 2 mL pre-packed vacuum flow Pb resin columns.

Effect of Methyl Substitution on the N-H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies.

PubMed

Sarkar, Shubhra; Ramanathan, N; Sundararajan, K

2018-03-08

Hydrogen-bonded interactions of pyrrole with water and methanol have been studied using matrix isolation infrared spectroscopy and compared with the calculation performed on dimethyl ether. Computations carried out at MP2/aug-cc-pVDZ level of theory yielded two minima for the pyrrole-water and pyrrole-methanol complexes. The global and local minima correspond to the N-H···O and O-H···π complexes, respectively, where the N-H group of pyrrole interacts with oxygen of water/methanol and O-H of water and methanol interacts with the π cloud of pyrrole. Computations performed on the pyrrole-dimethyl ether gave only N-H···O type complex. From the experimental vibrational wavenumber shifts in the N-H stretching and N-H bending modes of pyrrole, as well as in the O-H stretching modes of water and methanol, the 1:1 N-H···O complexes were discerned. The strength of the N-H···O hydrogen bond and the corresponding shift in the N-H stretching vibrational wavenumbers increases in the order pyrrole-water < pyrrole-methanol < pyrrole-dimethyl ether, where a proton is successively replaced by a methyl group. Apart from the 1:1 complexes, higher clusters of 2:1 and 1:2 pyrrole-water and pyrrole-methanol complexes were also generated in N 2 matrix. Atoms in molecules and natural bond orbital analyses were carried out at the MP2/aug-cc-pVDZ level to understand the nature of interaction in the 1:1 pyrrole-water, pyrrole-methanol and pyrrole-dimethyl ether complexes.

Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

NASA Astrophysics Data System (ADS)

Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

2016-09-01

We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

Adduct simplification in the analysis of cyanobacterial toxins by matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Howard, Karen L; Boyer, Gregory L

2007-01-01

A novel method for simplifying adduct patterns to improve the detection and identification of peptide toxins using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry is presented. Addition of 200 microM zinc sulfate heptahydrate (ZnSO(4) . 7H(2)O) to samples prior to spotting on the target enhances detection of the protonated molecule while suppressing competing adducts. This produces a highly simplified spectrum with the potential to enhance quantitative analysis, particularly for complex samples. The resulting improvement in total signal strength and reduction in the coefficient of variation (from 31.1% to 5.2% for microcystin-LR) further enhance the potential for sensitive and accurate quantitation. Other potential additives tested, including 18-crown-6 ether, alkali metal salts (lithium chloride, sodium chloride, potassium chloride), and other transition metal salts (silver chloride, silver nitrate, copper(II) nitrate, copper(II) sulfate, zinc acetate), were unable to achieve comparable results. Application of this technique to the analysis of several microcystins, potent peptide hepatotoxins from cyanobacteria, is illustrated. Copyright (c) 2007 John Wiley & Sons, Ltd.

Hexafluorobenzene in comparison with perfluoro-15-crown-5-ether for repeated monitoring of oxygenation using 19F MRI in a mouse model.

PubMed

Mignion, Lionel; Magat, Julie; Schakman, Olivier; Marbaix, Etienne; Gallez, Bernard; Jordan, Bénédicte F

2013-01-01

Hexafluorobenzene (HFB) and perfluoro-15-crown-5-ether (15C5) were compared as fluorine reporter probes of tissue oxygenation using (19)F MRI for dynamic assessment of muscle oxygenation, with special focus on muscle tissue toxicity of the probes, and consecutive alteration of animal behavior. The latter were also compared in terms of sensitivity to changes in oxygenation as well as of signal-to-noise ratio for accurate pO(2) measurements. For that purpose, mouse muscles were imaged at 11.7 T, at 2- and 36-h after intramuscular injection of HFB or 15C5. Histological analysis of the muscle tissue revealed a lack of toxicity for 15C5 from 2 up to 36-h postinjection, whereas HFB induced tissue necrosis, blood clots and thrombosis as soon as 24-h postinjection. This muscle toxicity led to a limitation in mice mobility 24-h after injection of HFB as evidenced by behavioral testing (open-field, grip strength, and catwalk tests), which was not the case after 15C5 intramuscular injection. Finally, pO(2) measurements assessed 2-h postinjection showed consistent values with both probes, evidencing cross-validation of the (19)F MRI oximetry technique for acute measurements. However, the measurement at 36-h was hampered for HFB, which showed significant lower values of muscle pO(2), whereas 15C5 was able to reliably assess muscle pO(2) at 36-h postinjection. Copyright © 2012 Wiley Periodicals, Inc.

Selective P4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes.

PubMed

Pelties, Stefan; Maier, Thomas; Herrmann, Dirk; de Bruin, Bas; Rebreyend, Christophe; Gärtner, Stefanie; Shenderovich, Ilya G; Wolf, Robert

2017-05-02

Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt 2 ) 2 {Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf) x {Co(cod) 2 }], reacts with P 4 to afford [{K(thf)} 2 {(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (2 a) in 61 % yield (isolated product). [{K(OEt 2 )} 2 {(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (2 b) and [K([18]crown-6)(MeCN)] 2 [{(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2 c). Oxidation of 2 a with [Cp 2 Fe]BAr F 4 (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt 2 ){(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (3 a) and [K(dme) 4 ][{(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (3 b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co} 2 (μ-η 4 :η 4 -P 4 )] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp 2 Fe]BAr F 4 . The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P 4 4- units sandwiched between {(BIAN)Co} fragments. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuz'mina, L. G.; Fedorova, O. A.; Andryukhina, E. N.

A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the {pi}-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobicmore » regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of {pi}-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.« less

Process for extracting technetium from alkaline solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

1995-01-01

A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

N-alkyl pyrrolidone ether podands as versatile alkali metal ion chelants.

PubMed

Perrin, Andrea; Myers, Dominic; Fucke, Katharina; Musa, Osama M; Steed, Jonathan W

2014-02-28

This work explores the coordination chemistry of a bis(pyrrolidone) ether ligand. Pyrrolidones are commercially important functional groups because of the high polarity and hence high hydrophilicity and surface affinity. An array of alkali metal ion complexes of a podand bearing two pendant pyrrolidone functionalities, namely 1-{2-[2-(2-oxo-pyrrolid-1-yl)-ethoxy]-ethyl}-pyrrolid-2-one (1) are reported. Reaction of this ligand with sodium hexafluorophosphate gives two discrete species of formulae [Na(1)2]PF6 (3) and [Na3(H2O)2(μ-1)2](PF6)3 (4), and a coordination polymer {[Na3(μ3-1)3(μ2-1)](PF6)3}n (5). The same reaction in methanol gives a 1 : 1 complex, namely [Na2(μ-1)2(MeOH)2](PF6)2 (6). Use of tetraphenyl borate as a less coordinating counter ion gives [Na2(1)2(H2O)4](BPh4)2 (7) and [Na2(1)4](BPh4)2 (8). Two potassium complexes have also been isolated, a monomer [K(1)2]PF6 (9) and a cyclic tetramer [K4(μ4-H2O)2(μ-1)4](PF6)4 (10). The structures illustrate the highly polar nature of the amide carbonyl moiety within bis(pyrrolidone) ethers with longer interactions to the ether oxygen atom. The zinc complex is also reported and {[ZnCl2(μ-1)]}n (11) exhibits bonding only to the carbonyl moieties. The ether oxygen atom is not necessary for Na(+) complexation as exemplified by the structure of the sodium complex of the analogue 1,3-bis(pyrrolid-2-on-1-yl)butane (2). Reaction of compound 1 with lithium salts results in isolation of the protonated ligand.

Preparation, Fabrication, and Evaluation of Advanced Polymeric and Composite Materials

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.

1997-01-01

The thesis titles are given below: physical and mechanical behavior of amorphous poly(arylene ether-co-imidasole)s and poly(arylene ether-co-imidasole) modification epoxies; the requirements of patentability as applied to the chemical arts; fabrication of thermoplastic polymer composite ribbon; blend of reactive diluents with phenylethynyl-terminated arylene ether oligomers; the synthesis, characterization, and application of ether-containing polyimides; the synthesis of reflective and electrically conductive polyimide films via an in-situ self-metalization procedure using silver (I) complexes; the thermal cure of phenylethynyl terminated polyimides and selected model compounds; and the synthesis, characterization, and molecular modeling of cyclic arylene ether oligomers.

Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, Susan K; Gordon, John C; Thorn, David L

2009-01-01

The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress hasmore » been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), and 1,2-diphenyl-2-methoxyethanol (C) (Figure 1). Reaction of (dipic)V{sup V}(O)O{sup i}Pr (1a) or (dipic)V{sup v}(O)OEt (lb) with A, B, or C in acetonitrile yielded new vanadium(V) complexes where the alcohol-ether ligand was bound in a chelating fashion. From the reaction of 1b with pinacol monomethyl ether (A) in acetonitrile solution, (dipic)V{sup v}(O)(pinOMe) (2) (PinOMe = 2,3-dimethyl-3-methoxy-2-butanoxide) was isolated in 61 % yield. Reaction of 1b with 2-phenoxyethanol (B) in acetonitrile gave the new complex (dipic)V{sup v}(O)(OPE) (3) (OPE = 2-phenoxyethoxide), which was isolated in 76% yield. In a similar fashion, 1a reacted with 1,2-diphenyl-2-methoxyethanol (C) to give (dipic)V(O)(DPME) (4) (DPME = 1,2-diphenyl-2-methoxyethoxide), which was isolated in 39% yield. Complexes 2, 3, and 4 were characterized by {sup 1}H NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Compared to the previously reported vanadium(V) pinacolate complex (dipic)V(O)(pinOH) the X-ray structure of complex 2 reveals a slightly shorter V = O bond, 1.573(2) {angstrom} vs 1.588(2) {angstrom} for the pinOH structure. Complexes 3 and 4 display similar vanadium oxo bond distances of 1.568(2) {angstrom} and 1.576(2) {angstrom}, respectively. All three complexes show longer bonds to the ether-oxygen trans to the oxo (2.388(2) {angstrom} for 2, 2.547(2) {angstrom} for 3, and 2.438(2) {angstrom} for 4) than to the hydroxy-oxygen in the pinOH structure (2.252(2) {angstrom}).« less

FTIR cryospectroscopic and ab initio studies of desflurane-dimethyl ether H-bonded complexes.

PubMed

Melikova, S M; Rutkowski, K S; Rospenk, M

2017-09-05

The IR spectra of mixtures of desflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Kr at T~118-158K. Comparative analysis of the experimental data and results of ab initio calculations show that either of the two C-H groups of desflurane is involved in heterodimer formation of comparable strengths. The blue frequency shift is found for stretching vibrations of those C-H donors which directly participate in H-bond formation. Additionally the complexes are stabilized by weaker contacts between hydrogen atoms of dimethyl ether and fluorine atoms of desflurane. Copyright © 2017 Elsevier B.V. All rights reserved.

Ion sensing by charge transfer absorption variations of benzocrown-bipyridinium conjugates with an alkyl chain.

PubMed

Kuwabara, Tetsuo; Satake, Ryota; Guo, Haocheng

2015-01-01

Two benzocrown ether-bipyridinium conjugates, 1 and 2, each having a different length of alkyl chains with butyl and dodecyl groups, respectively, have been synthesized for the purpose of developing a new guest-responsive color-change chemosensor. Both 1 and 2 showed yellow colors with broad absorption bands around 400 nm in acetonitrile. These are associated with the intramolecular charge transfer (CT) absorption, in which the benzocrown ether and bipyridinium units act as the donor and acceptor, respectively. Upon addition of the guest; such as Na(+), they faded in color due to the blue shift in their intramolecular charge transfer absorption bands. These are associated with the formation of 1:1 host-guest inclusion complex. Analogues, 3 and 4, both being similar in structure to 1 and 2 with non-crown ether unit, also showed intramolecular CT absorptions around 400 nm, but did not change their absorption spectra upon addition of the guest because of the lack of guest-binding abilities. The guest-induced color change of 1 and 2 can be used for alkali and alkaline metal ion sensing. Both 1 and 2 could detect divalent cations such as Mg(2+) and Ca(2+) rather than univalent ones, Li(+), Na(+), K(+), Rb(+), and Cs(+). Although a marked difference between 1 and 2 was not observed in their guest sensing abilities, the remarkable recognition of 1 and 2 for Mg(2+) and Ca(2+) was found compared with that of 5, which has benzyl unit instead of alkyl chains of 1 and 2. The sensitivity values of 1 and 2 were roughly proportional to their binding constants, as shown by the binding constants with Li(+), Na(+), Mg(2+), and Ca(2+) with the values of 910, 260, 820, and 2300 M(-1) for 1 and 930, 290, 1270, and 2790 M(-1) for 2, while the binding constants of 5 were estimated to be 930, 440, 210, and 1200 M(-1) for Li(+), Na(+), Mg(2+), and Ca(2+), respectively. The limit concentration of detection of 2 for Ca(2+) was estimated to be 0.016 mM, which was the smallest value in this system.

Synergistic adsorption of heavy metal ions and organic pollutants by supramolecular polysaccharide composite materials from cellulose, chitosan and crown ether

PubMed Central

Mututuvari, Tamutsiwa M.; Tran, Chieu D.

2013-01-01

We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm+Cl−], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm+Cl−] used was recovered for reuse, the method is recyclable. The [CEL/CS + B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS + B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd2+, Zn2+ and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd2+ and Zn2+ by [CS + B15C5], [CEL + B15C5] and [CEL + CS + B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd2+ (or Zn2+), and as a consequence, the [CS + B15C5] (or the [CEL + B15C5]) composite can adsorb relatively larger amount Cd2+ (or Zn2+). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS + CEL + B15C5] composites to be reused with similar adsorption efficiency. PMID:24333678

Using stand-level optimization to reduce crown fire hazard

Treesearch

David H. Graetz; John Sessions; Steven L. Garman

2007-01-01

This study evaluated the ability to generate prescriptions for a wide variety of stands when the goal is to reduce crown fire potential. Forest managers charged with reducing crown fire potential while providing for commodity and ecological production have been hampered by the complexity of possible management options. A program called Stand-Level Optimization with...

Effect of the crown design and interface lute parameters on the stress-state of a machined crown-tooth system: a finite element analysis.

PubMed

Shahrbaf, Shirin; vanNoort, Richard; Mirzakouchaki, Behnam; Ghassemieh, Elaheh; Martin, Nicolas

2013-08-01

The effect of preparation design and the physical properties of the interface lute on the restored machined ceramic crown-tooth complex are poorly understood. The aim of this work was to determine, by means of three-dimensional finite element analysis (3D FEA) the effect of the tooth preparation design and the elastic modulus of the cement on the stress state of the cemented machined ceramic crown-tooth complex. The three-dimensional structure of human premolar teeth, restored with adhesively cemented machined ceramic crowns, was digitized with a micro-CT scanner. An accurate, high resolution, digital replica model of a restored tooth was created. Two preparation designs, with different occlusal morphologies, were modeled with cements of 3 different elastic moduli. Interactive medical image processing software (mimics and professional CAD modeling software) was used to create sophisticated digital models that included the supporting structures; periodontal ligament and alveolar bone. The generated models were imported into an FEA software program (hypermesh version 10.0, Altair Engineering Inc.) with all degrees of freedom constrained at the outer surface of the supporting cortical bone of the crown-tooth complex. Five different elastic moduli values were given to the adhesive cement interface 1.8GPa, 4GPa, 8GPa, 18.3GPa and 40GPa; the four lower values are representative of currently used cementing lutes and 40GPa is set as an extreme high value. The stress distribution under simulated applied loads was determined. The preparation design demonstrated an effect on the stress state of the restored tooth system. The cement elastic modulus affected the stress state in the cement and dentin structures but not in the crown, the pulp, the periodontal ligament or the cancellous and cortical bone. The results of this study suggest that both the choice of the preparation design and the cement elastic modulus can affect the stress state within the restored crown-tooth complex. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A fluorescent combinatorial logic gate with Na+, H+-enabled OR and H+-driven low-medium-high ternary logic functions.

PubMed

Spiteri, Jasmine M A; Mallia, Carl J; Scerri, Glenn J; Magri, David C

2017-12-06

A novel fluorescent molecular logic gate with a 'fluorophore-spacer 1 -receptor 1 -spacer 2 -receptor 2 ' format is demonstrated in 1 : 1 (v/v) methanol/water. The molecule consists of an anthracene fluorophore, and tertiary alkyl amine and N-(2-methoxyphenyl)aza-15-crown-5 ether receptors. In the presence of threshold concentrations of H + and Na + , the molecule switches 'on' as an AND logic gate with a fluorescence quantum yield of 0.21 with proton and sodium binding constants of log β H+ = 9.0 and log β Na+ = 3.2, respectively. At higher proton levels, protonation also occurs at the anilinic nitrogen atom ether with a log β H+ = 4.2, which allows for Na + , H + -enabled OR (OR + AND circuit) and H + -driven ternary logic functions. The reported molecule is compared and contrasted to classic anthracene-based Na + and H + logic gates. We propose that such logic-based molecules could be useful tools for probing the vicinity of Na + , H + antiporters in biological systems.

Nuclear chemistry research and spectroscopy with radioactive sources. Sixteenth annual progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fink, R.W.

1980-10-31

Nuclear spectroscopic studies included the decay of /sup 201/Po to /sup 201/Bi, decay of /sup 201/At, decay of /sup 187/Au, and g/sub 7/2/ intruder band in /sup 109/Ag. A systematic comparison was conducted of the Interacting Boson-Fermion Approximation model predictions with experiment on neutron-deficient odd-A gold isotopes. An international comparison of /sup 133/Ba ..gamma..-ray standards was completed. L/sub 1/, L/sub 2/, and L/sub 3/ subshells were studied, and the decay energy of /sup 207/Bi is being measured. Carrier-free /sup 18/F has been prepared in crown ether solution. (DLC)

Supercritical fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth

1994-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Thermodynamics and kinetics of gas storage in porous liquids

DOE PAGES

Zhang, Fei; Yang, Fengchang; Huang, Jingsong; ...

2016-07-05

The recent synthesis of organic molecular liquids with permanent porosity (Giri et al., Nature, 2015, 527, 216) opens up exciting new avenues for gas capture, storage, and separation. Using molecular dynamics simulations, we study the thermodynamics and kinetics for the storage of CH 4, CO 2, and N 2 molecules in porous liquids consisting of crown-ether substituted cage molecules in a 15-crown-5 solvent. It is found that the gas storage capacity per cage molecule follows the order of CH 4 > CO 2 > N 2, which does not correlate simply with the size of gas molecules. Different gas moleculesmore » are stored inside the cage differently, e.g., CO 2 molecules prefer the cage s core while CH 4 molecules favor both the core and the branch regions. All gas molecules considered can enter the cage essentially without energy barriers, and their dynamics inside the cage are only slightly hindered by the nanoscale confinement. In addition, all gas molecules can leave the cage on nanosecond time scale by overcoming a modest energy penalty. The molecular mechanisms of these observations are clarified.« less

Thermodynamics and kinetics of gas storage in porous liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fei; Yang, Fengchang; Huang, Jingsong

The recent synthesis of organic molecular liquids with permanent porosity (Giri et al., Nature, 2015, 527, 216) opens up exciting new avenues for gas capture, storage, and separation. Using molecular dynamics simulations, we study the thermodynamics and kinetics for the storage of CH 4, CO 2, and N 2 molecules in porous liquids consisting of crown-ether substituted cage molecules in a 15-crown-5 solvent. It is found that the gas storage capacity per cage molecule follows the order of CH 4 > CO 2 > N 2, which does not correlate simply with the size of gas molecules. Different gas moleculesmore » are stored inside the cage differently, e.g., CO 2 molecules prefer the cage s core while CH 4 molecules favor both the core and the branch regions. All gas molecules considered can enter the cage essentially without energy barriers, and their dynamics inside the cage are only slightly hindered by the nanoscale confinement. In addition, all gas molecules can leave the cage on nanosecond time scale by overcoming a modest energy penalty. The molecular mechanisms of these observations are clarified.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fei; He, Yadong; Huang, Jingsong

Porous liquids are a promising new class of materials featuring nanoscale cavity units dispersed in liquids that are suitable for applications such as gas storage and separation. In this work, we use molecular dynamics simulations to examine the multicomponent gas storage in a porous liquid consisting of crown-ether-substituted cage molecules dissolved in a 15-crown-5 solvent. We compute the storage of three prototypical small molecules including CO 2, CH 4, and N 2 and their binary mixtures in individual cage molecules. For porous liquids in equilibrium with a binary 1:1 gas mixture bath with partial gas pressure of 27.5 bar, amore » cage molecule shows a selectivity of 4.3 and 13.1 for the CO 2/CH 4 and CO 2/N 2 pairs, respectively. We provide a molecular perspective of how gas molecules are stored in the cage molecule and how the storage of one type of gas molecule is affected by other types of gas molecules. Finally, our results clarify the molecular mechanisms behind the selectivity of such cage molecules toward different gases.« less

Multicomponent Gas Storage in Organic Cage Molecules

DOE PAGES

Zhang, Fei; He, Yadong; Huang, Jingsong; ...

2017-05-18

Porous liquids are a promising new class of materials featuring nanoscale cavity units dispersed in liquids that are suitable for applications such as gas storage and separation. In this work, we use molecular dynamics simulations to examine the multicomponent gas storage in a porous liquid consisting of crown-ether-substituted cage molecules dissolved in a 15-crown-5 solvent. We compute the storage of three prototypical small molecules including CO 2, CH 4, and N 2 and their binary mixtures in individual cage molecules. For porous liquids in equilibrium with a binary 1:1 gas mixture bath with partial gas pressure of 27.5 bar, amore » cage molecule shows a selectivity of 4.3 and 13.1 for the CO 2/CH 4 and CO 2/N 2 pairs, respectively. We provide a molecular perspective of how gas molecules are stored in the cage molecule and how the storage of one type of gas molecule is affected by other types of gas molecules. Finally, our results clarify the molecular mechanisms behind the selectivity of such cage molecules toward different gases.« less

Magnetic blocking at 10 K and a dipolar-mediated avalanche in salts of the bis(η8-cyclooctatetraenide) complex [Er(COT)2]-.

PubMed

Meihaus, Katie R; Long, Jeffrey R

2013-11-27

The structures and magnetic properties of [K(18-crown-6)](+) (1) and [K(18-crown-6)(THF)2](+) (2) salts of the η(8)-cyclooctatetraenide sandwich complex [Er(COT)2](-) (COT(2-) = cyclooctatetraene dianion) are reported. Despite slight differences in symmetry, both compounds exhibit slow magnetic relaxation under zero applied dc field with relaxation barriers of ∼150 cm(-1) and waist-restricted magnetic hysteresis. Dc relaxation and dilution studies suggest that the drop in the magnetic hysteresis near zero field is influenced by a bulk magnetic avalanche effect coupled with tunneling of the magnetization. Through dilution with [K(18-crown-6)(THF)2][Y(COT)2] (3), these phenomena are substantially quenched, resulting in an open hysteresis loop to 10 K. Importantly, this represents the highest blocking temperature yet observed for a mononuclear complex and the second highest for any single-molecule magnet. A comprehensive comparative analysis of the magnetism of [K(18-crown-6)][Ln(COT)2] (Ln = Sm, Tb, Dy, Ho, Yb) reveals slow relaxation only for [K(18-crown-6)][Dy(COT)2] (4) with weak temperature dependence. Collectively, these results highlight the utility of an equatorial ligand field for facilitating slow magnetic relaxation in the prolate Er(III) ion.

Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

NASA Astrophysics Data System (ADS)

Zhang, Shiyi

The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug conjugate by densely attaching the polyphosphoester block with azide-functionalized Paclitaxel by azide-alkyne Huisgen cycloaddition. This Paclitaxel drug conjugate provides a powerful platform for combinational cancer therapy and bioimaging due to its ultra-high Paclitaxel loading (> 65 wt%), high water solubility (>6.2 mg/mL for PTX) and easy functionalization. Another polyphosphoester-based nanoparticle system has been developed by a programmable process for the rapid and facile preparation of a family of nanoparticles with different surface charges and functionalities. The non-ionic, anionic, cationic and zwitterionic nanoparticles with hydrodynamic diameters between 13 nm to 21 nm and great size uniformity could be rapidly prepared from small molecules in 6 h or 2 days. The anionic and zwitterionic nanoparticles were designed to load silver ions to treat pulmonary infections, while the cationic nanoparticles are being applied to regulate lung injuries by serving as a degradable iNOS inhibitor conjugates. In addition, a direct synthesis of acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an improved two-step preparation of polyphosphoester ionomer by acid-assisted cleavage of phosphoramidate bonds on polyphosphoramidate were developed. Polyphosphoramidate and polyphosphoester ionomers may be applied to many applications, due to their unique chemical and physical properties.

STRUCTURES AND BINDING ENERGIES OF METHYL TERT-BUTYL ETHER-WATER COMPLEXES

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is a well-known environmental contaminant owing to its high solubility in water. Since the early 1990s, MTBE has been added to gasoline to improve air quality in some metropolitan areas of the United States. Improved air quality was, however, achiev...

Synthesis and characterization of water-soluble hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins).

PubMed

Buchanan, Charles M; Alderson, Susan R; Cleven, Curtis D; Dixon, Daniel W; Ivanyi, Robert; Lambert, Juanelle L; Lowman, Douglas W; Offerman, Rick J; Szejtli, Jozsef; Szente, Lajos

2002-03-15

We have examined the synthesis of hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins) and the ability of these cyclodextrin ethers to form guest-host complexes with guest molecules. The hydroxybutenyl cyclodextrin ethers were prepared by a base-catalyzed reaction of 3,4-epoxy-1-butene with the parent cyclodextrins in an aqueous medium. Reaction byproducts were removed by nanofiltration before the hydroxybutenyl cyclodextrins were isolated by co-evaporation of water-EtOH. Hydroxybutenyl cyclodextrins containing no unsubstituted parent cyclodextrin typically have a degree of substitution of 2-4 and a molar substitution of 4-7. These hydroxybutenyl cyclodextrins are randomly substituted, amorphous solids. The hydroxybutenyl cyclodextrin ethers were found to be highly water soluble. Complexes of HBen-beta-CD with glibenclamide and ibuprofen were prepared and isolated. In both cases, the guest content of the complexes was large, and a significant increase in the solubility of the free drug was observed. Dissolution of the complexes in pH 1.4 water was very rapid, and significant increases in the solubility of the free drugs were observed. Significantly, after reaching equilibrium concentration, a decrease in the drug concentration over time was not observed.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri

1997-01-01

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and ortho-Sulfinyl Carbanions.

PubMed

Rodríguez, Ricardo I; Ramírez, Elsie; Yuste, Francisco; Sánchez-Obregón, Rubén; Alemán, José

2018-02-16

The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp-Csp 3 bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) of the ortho-sulfinylbenzyl carbanions, followed by elimination of the arylsulfonyl moiety. The scope of this alkynylation reaction is also discussed. Moreover, the development of a new approach for the synthesis of optically active tertiary benzylpropargyl alcohols is described, discussing the possible stereocourse of the reaction so as the influence of the ether 18-crown-6 and steric importance of acetylenic substituent.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.

1997-09-09

Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Gas Phase Conformations and Methyl Internal Rotation for 2-PHENYLETHYL Methyl Ether and its Argon Van Der Waals Complex from Fourier Transform Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Gurusinghe, Ranil M.; Tubergen, Michael

2015-06-01

A mini-cavity microwave spectrometer was used to record the rotational spectra arising from 2-phenylethyl methyl ether and its weakly bonded argon complex in the frequency range of 10.5 - 22 GHz. Rotational spectra were found for two stable conformations of the monomer: anti-anti and gauche-anti, which are 1.4 kJ mol-1 apart in energy at wB97XD/6-311++G(d,p) level. Doubled rotational transitions, arising from internal motion of the methyl group, were observed for both conformers. The program XIAM was used to fit the rotational constants, centrifugal distortion constants, and barrier to internal rotation to the measured transition frequencies of the A and E internal rotation states. The best global fit values of the rotational constants for the anti-anti conformer are A= 3799.066(3) MHz, B= 577.95180(17) MHz, C= 544.7325(3) MHz and the A state rotational constants of the gauche-anti conformer are A= 2676.1202(7) MHz, B= 760.77250(2) MHz, C= 684.78901(2) MHz. The rotational spectrum of 2-phenylethyl methyl ether - argon complex is consistent with the geometry where argon atom lies above the plane of the benzene moiety of gauche-anti conformer. Tunneling splittings were too small to resolve within experimental accuracy, likely due to an increase in three fold potential barrier when the argon complex is formed. Fitted rotational constants are A= 1061.23373(16) MHz, B= 699.81754(7) MHz, C= 518.33553(7) MHz. The lowest energy solvated ether - water complex with strong intermolecular hydrogen bonding has been identified theoretically. Progress on the assignment of the water complex will also be presented.

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

PubMed

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.

Chemoselective formation of unsymmetrically substituted ethers from catalytic reductive coupling of aldehydes and ketones with alcohols in aqueous solution.

PubMed

Kalutharage, Nishantha; Yi, Chae S

2015-04-03

A well-defined cationic Ru-H complex catalyzes reductive etherification of aldehydes and ketones with alcohols. The catalytic method employs environmentally benign water as the solvent and cheaply available molecular hydrogen as the reducing agent to afford unsymmetrical ethers in a highly chemoselective manner.

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

PubMed

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.

Sulfobutyl ether β-cyclodextrin (Captisol(®) ) and methyl β-cyclodextrin enhance and stabilize fluorescence of aqueous indocyanine green.

PubMed

DeDora, Daniel J; Suhrland, Cassandra; Goenka, Shilpi; Mullick Chowdhury, Sayan; Lalwani, Gaurav; Mujica-Parodi, Lilianne R; Sitharaman, Balaji

2016-10-01

As the only FDA-approved near-infrared fluorophore, indocyanine green (ICG) is commonly used to image vasculature in vivo. ICG degrades rapidly in solution, which limits its usefulness in certain applications, including time-sensitive surgical procedures. We propose formulations that address this shortcoming via complexation with β-cyclodextrin derivatives (β-CyD), which are known to create stabilizing inclusion complexes with hydrophobic molecules. Here, we complexed ICG with highly soluble methyl β-CyD and FDA-approved sulfobutyl ether β-CyD (Captisol(®) ) in aqueous solution. We measured the fluorescence of the complexes over 24 h. We found that both CyD+ICG complexes exhibit sustained fluorescence increases of >2.0× versus ICG in water and >20.0× in PBS. Using transmission electron microscopy, we found evidence of reduced aggregation in complexes versus ICG alone. We thus conclude that this reduction in aggregation helps mitigate fluorescence autoquenching of CyD+ICG complexes compared in ICG alone. We also found that while ICG complexed with methyl β-CyD severely reduced the viability of MRC-5 fibroblasts, ICG complexed with sulfobutyl ether β-CyD had no effect on viability. These results represent an important first step toward enhancing the utility of aqueous ICG by reducing aggregation-dependent fluorescence degradation. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1457-1464, 2016. © 2015 Wiley Periodicals, Inc.

Oxime ether lipids containing hydroxylated head groups are more superior siRNA delivery agents than their nonhydroxylated counterparts.

PubMed

Gupta, Kshitij; Mattingly, Stephanie J; Knipp, Ralph J; Afonin, Kirill A; Viard, Mathias; Bergman, Joseph T; Stepler, Marissa; Nantz, Michael H; Puri, Anu; Shapiro, Bruce A

2015-01-01

To evaluate the structure-activity relationship of oxime ether lipids (OELs) containing modifications in the hydrophobic domains (chain length, degree of unsaturation) and hydrophilic head groups (polar domain hydroxyl groups) toward complex formation with siRNA molecules and siRNA delivery efficiency of resulting complexes to a human breast cancer cell line (MDA-MB-231). Ability of lipoplex formation between oxime ether lipids with nucleic acids were examined using biophysical techniques. The potential of OELs to deliver nucleic acids and silence green fluorescent protein (GFP) gene was analyzed using MDA-MB-231 and MDA-MB-231/GFP cells, respectively. Introduction of hydroxyl groups to the polar domain of the OELs and unsaturation into the hydrophobic domain favor higher transfection and gene silencing in a cell culture system.

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

NASA Astrophysics Data System (ADS)

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%.

Human exposure to PCDDs and their precursors from heron and tern eggs in the Yangtze River Delta indicate PCP origin.

PubMed

Zhou, Yihui; Yin, Ge; Asplund, Lillemor; Stewart, Kathryn; Rantakokko, Panu; Bignert, Anders; Ruokojärvi, Päivi; Kiviranta, Hannu; Qiu, Yanling; Ma, Zhijun; Bergman, Åke

2017-06-01

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic to humans and wildlife. In the present study, PCDD/Fs were analyzed in the eggs of whiskered terns (Chlidonias hybrida), and genetically identified eggs from black-crowned night herons (Nycticorax nycticorax) sampled from two lakes in the Yangtze River Delta area, China. The median toxic equivalent (TEQ) of PCDD/Fs were 280 (range: 95-1500) and 400 (range: 220-1100) pg TEQ g -1 lw (WHO, 1998 for birds) in the eggs of black-crowned night heron and whiskered tern, respectively. Compared to known sources, concentrations of PCDDs relative to the sum of PCDD/Fs in bird eggs, demonstrated high abundance of octachlorodibenzo-p-dioxin (OCDD), 1,2,3,4,6,7,8-heptaCDD and 1,2,3,6,7,8-hexaCDD indicating pentachlorophenol (PCP), and/or sodium pentachlorophenolate (Na-PCP) as significant sources of the PCDD/Fs. The presence of polychlorinated diphenyl ethers (PCDEs), hydroxylated and methoxylated polychlorinated diphenyl ethers (OH- and MeO-PCDEs, known impurities in PCP products), corroborates this hypothesis. Further, significant correlations were found between the predominant congener CDE-206, 3'-OH-CDE-207, 2'-MeO-CDE-206 and OCDD, indicating a common origin. Eggs from the two lakes are sometimes used for human consumption. The WHO health-based tolerable intake of PCDD/Fs is exceeded if eggs from the two lakes are consumed regularly on a weekly basis, particularly for children. The TEQs extensively exceed maximum levels for PCDD/Fs in hen eggs and egg products according to EU legislation (2.5 pg TEQ g -1 lw). The results suggest immediate action should be taken to manage the contamination, and further studies evaluating the impacts of egg consumption from wild birds in China. Likewise, studies on dioxins and other POPs in common eggs need to be initiated around China. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

EPA Science Inventory

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)....

Metabolite characterization of a novel anti-cancer agent, icotinib, in humans through liquid chromatography/quadrupole time-of-flight tandem mass spectrometry.

PubMed

Liu, Dongyang; Jiang, Ji; Zhang, Li; Tan, Fenlai; Wang, Yingxiang; Hu, Pei

2011-08-15

Icotinib is a novel anti-cancer drug that has shown promising clinical efficacy and safety in patients with non-small-cell lung cancer (NSCLC). At this time, the metabolic fate of icotinib in humans is unknown. In the present study, a liquid chromatography/quadrupole time-of-flight tandem mass spectrometry (LC/Q-TOF MS) method was established to characterize metabolites of icotinib in human plasma, urine and feces. In addition, nuclear magnetic resonance (NMR) detection was utilized to determine the connection between side-chain and quinazoline groups for some complex metabolites. In total, 29 human metabolites (21 isomer metabolites) were characterized, of which 23 metabolites are novel compared to the metabolites in rats. This metabolic study revealed that icotinib was extensively metabolized at the 12-crown-4 ether moiety (ring-opening and further oxidation), carbon 15 (hydroxylation) and an acetylene moiety (oxidation) to yield 19 oxidized metabolites and to further form 10 conjugates with sulfate acid or glucuronic acid. To our knowledge, this is the first report of the human metabolic profile of icotinib. Study results indicated that significant attention should be paid to the metabolic profiles of NSCLC patients during the development of icotinib. Copyright © 2011 John Wiley & Sons, Ltd.

Antibacterial activity of plant defensins against alfalfa crown rot pathogens

USDA-ARS?s Scientific Manuscript database

Alfalfa (Medicago sativa) is the fourth most widely grown crop in the United States. Alfalfa crown rot is a disease complex that severely decreases alfalfa stand density and productivity in all alfalfa-producing areas. Currently, there are no viable methods of disease control. Plant defensins are sm...

Reduction-resistant and reduction-catalytic double-crown nickel nanoclusters

NASA Astrophysics Data System (ADS)

Zhu, Min; Zhou, Zhou, Shiming; Yao, Chuanhao; Liao, Lingwen; Wu, Zhikun

2014-11-01

In this work, an attempt to synthesize zero-valent Ni nanoclusters using the Brust method resulted in an unexpected material, Ni6(SCH2CH2Ph)12, which is a nanoscale Ni(ii)-phenylethanethiolate complex and a hexameric, double-crown-like structure, as determined by a series of characterizations, including mass spectrometry (MS), thermal gravimetric analysis (TGA), single-crystal X-ray diffraction (XRD), and X-ray photoelectron spectrometry (XPS). An interesting finding is that this complex is resistant to aqueous BH4-. Investigations into other metal-phenylethanethiolate and Ni-thiolate complexes reveal that this property is not universal and appears only in complexes with a double-crown-like structure, indicating the correlation between this interesting property and the complexes' special structure. Another interesting finding is that the reduction-resistant Ni6(SCH2CH2Ph)12 exhibits remarkably higher catalytic activity than a well-known catalyst, Au25(SCH2CH2Ph)18, toward the reduction of 4-nitrophenol at low temperature (e.g., 0 °C). This work will help stimulate more research on the properties and applications of less noble metal nanoclusters.In this work, an attempt to synthesize zero-valent Ni nanoclusters using the Brust method resulted in an unexpected material, Ni6(SCH2CH2Ph)12, which is a nanoscale Ni(ii)-phenylethanethiolate complex and a hexameric, double-crown-like structure, as determined by a series of characterizations, including mass spectrometry (MS), thermal gravimetric analysis (TGA), single-crystal X-ray diffraction (XRD), and X-ray photoelectron spectrometry (XPS). An interesting finding is that this complex is resistant to aqueous BH4-. Investigations into other metal-phenylethanethiolate and Ni-thiolate complexes reveal that this property is not universal and appears only in complexes with a double-crown-like structure, indicating the correlation between this interesting property and the complexes' special structure. Another interesting finding is that the reduction-resistant Ni6(SCH2CH2Ph)12 exhibits remarkably higher catalytic activity than a well-known catalyst, Au25(SCH2CH2Ph)18, toward the reduction of 4-nitrophenol at low temperature (e.g., 0 °C). This work will help stimulate more research on the properties and applications of less noble metal nanoclusters. Electronic supplementary information (ESI) available: Experimental section, detailed structural data, MS analyses of M-SCH2CH2Ph complexes, stability study of Ni6 and TGA analysis of Au25(SCH2CH2Ph)18. See DOI: 10.1039/c4nr04981k

Synthesis and blood pressure lowering activity of benzylic ethers of 2-diethylaminoethanol and a related diamine.

PubMed

El-Antably, S M; Soine, T O; Shaath, N A; Gupta, P K

1975-08-01

Based upon the unpublished finding that 3'-hydroxy-4'-(beta-diethylaminoethoxy)-3',4'-dihydroseselin possessed a potent blood pressure lowering effect in the cat at a dose of 1 mg/kg, the present study examined the activities of several related compounds. These compounds were derived by dissection of the parent compound to give four benzylic ethers of 2-diethylaminoethanol and a diamine, derived by replacing the ether oxygen of the parent compound with an N--CH3 function. The simplest compounds were the benzyl and 2,6-dimethoxybenzyl ethers of the aminoalcohol. Closely related to the benzyl compound was a congener with a hydroxymethyl group on the benzylic carbon. The beta-diethylaminoethyl ether of 4-chromanol was the most complex of the ethers. The blood pressure measurements were carried out on male cats and compared to papaverine hydrochloride as a standard. In all cases, the most potent blood pressure lowering activity resided in the parent compound, which was not greatly superior to the diamine but substantially more active than the other compounds.

Oxime ether lipids containing hydroxylated head groups are more superior siRNA delivery agents than their nonhydroxylated counterparts

PubMed Central

Gupta, Kshitij; Mattingly, Stephanie J; Knipp, Ralph J; Afonin, Kirill A; Viard, Mathias; Bergman, Joseph T; Stepler, Marissa; Nantz, Michael H; Puri, Anu; Shapiro, Bruce A

2015-01-01

Aim: To evaluate the structure–activity relationship of oxime ether lipids (OELs) containing modifications in the hydrophobic domains (chain length, degree of unsaturation) and hydrophilic head groups (polar domain hydroxyl groups) toward complex formation with siRNA molecules and siRNA delivery efficiency of resulting complexes to a human breast cancer cell line (MDA-MB-231). Materials & methods: Ability of lipoplex formation between oxime ether lipids with nucleic acids were examined using biophysical techniques. The potential of OELs to deliver nucleic acids and silence green fluorescent protein (GFP) gene was analyzed using MDA-MB-231 and MDA-MB-231/GFP cells, respectively. Results & conclusion: Introduction of hydroxyl groups to the polar domain of the OELs and unsaturation into the hydrophobic domain favor higher transfection and gene silencing in a cell culture system. PMID:26107486

Electrochemical, spectral, and computational studies of metalloporphyrin dimers formed by cation complexation of crown ether cavities.

PubMed

Chitta, Raghu; Rogers, Lisa M; Wanklyn, Amber; Karr, Paul A; Kahol, Pawan K; Zandler, Melvin E; D'Souza, Francis

2004-11-01

The effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)ClO(4) by differential pulse voltammetry technique. The HOMO--LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K(4)(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K(+) induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu--Cu < VO--VO < Ag--Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO--LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K(4)(MTCP)(2) were observed. A reduced HOMO--LUMO gap predicted for the dimer by B3LYP/(3-21G(), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.

Synthesis, Electrochemistry, and Reactivity of the Actinide Trisulfides [K(18-crown-6)][An(η(3)-S3)(NR2)3] (An = U, Th; R = SiMe3).

PubMed

Smiles, Danil E; Wu, Guang; Hayton, Trevor W

2016-09-19

The reaction of [Th(I)(NR2)3] (R = SiMe3) with [K(18-crown-6)]2[S4] results in the formation of [K(18-crown-6)][Th(η(3)-S3)(NR2)3] (2). Oxidation of 2, or its uranium analogue, [K(18-crown-6)][U(η(3)-S3)(NR2)3] (1), with AgOTf, in an attempt to generate an [S3](•-) complex, results in the formation of [K(18-crown-6)][An(OTf)2(NR2)3] (3, An = U; 4, An = Th) as the only isolable products. These results suggest that the putative [S3](•-) ligand is only weakly coordinating and can be easily displaced by nucleophiles.

Furo-fused BINOL based crown as a fluorescent chiral sensor for enantioselective recognition of phenylethylamine and ethyl ester of valine.

PubMed

Upadhyay, Sunil P; Pissurlenkar, Raghuvir R S; Coutinho, Evans C; Karnik, Anil V

2007-07-20

A furo-fused BINOL based chiral crown was developed as an enantioselective chiral sensor for phenylethylamine and ethyl ester of valine. Fusion of furan to BINOL has resulted in a highly stereo-discriminating backbone for the chiral crown developed. This chiral crown exhibited a fluorescence enhancement difference of 2.97 times between two enantiomers of phenylethylamine and 2.55 times between two enantiomers of ethyl ester of valine. The ratio of association constants for two diastereomeric complexes of two enantiomers of phenylethylamine was found to be 11.30, and the ratio for two enantiomers of ethyl ester of valine was 7.02.

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

PubMed Central

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

2016-01-01

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. PMID:26628518

Practical Stereochemistry.

PubMed

Kellogg, Richard M

2017-04-18

The relationship between fundamental and applied is often uneasy, particularly in modern political climates. A familiar political view, aimed negatively at the scientific community, is that the former is a waste of money whereas the latter gives value for investment. The answer that fundamental is required as the basis for practical suffers from the fact that the timelines between fundamental and practical are often long and the routes contorted and unexpected. This has been my experience. In this Account, examples are given from the research in which I have been involved wherein quite fundamental considerations have led to various applications. The longer the time, the clearer and broader the relationship. Fundamental can and does lead to application. They need and depend on each other. I have seen this both from the side of academia and from small companies. In the course of the past 40 plus years, I have been involved in various aspects of stereochemistry and, in particular, chirality. It has been rewarding to see that several of the developments, most originally grounded in fundamental research considerations, have been used in the chemical community and given new dimensions and often practical applications by others. In this Account, a path-not planned deliberately by me-from orbital symmetry and Woodward-Hoffmann rules through crown ethers to conformational analysis to diastereomeric resolutions to deracemizations powered by Ostwald ripening and the Gibbs-Thomson effect to nucleation to helicenes is described. In order of discussion, the orbital symmetry aspects have via an unusual and unpredicted path has resulted in, among other things, a synthesis of hindered alkenes useful for the production of molecular motors. The crown ether aspects led to discovery of the utility of cesium salts particularly for racemization sensitive nucleophilic substitutions. Work on diastereomeric resolutions has concentrated on the mechanistic as well as practical/commercial aspects of the use of multiple resolving agents (Dutch resolution). During this work the complex relationship between nucleation and chirality in diastereomeric resolutions began to reveal itself. In general, nucleation, especially with involvement of chirality, is a topical challenge that has attracted the attention of many groups. The contribution of this knowledge to the development of attrition driven deracemizations of racemizable conglomerates is described. This remarkable technology allows, without intervention of chiral aids, conversion of certain racemates in quantitative yield and absolute enantiomeric excess to a single enantiomer. From a practical standpoint, this methodology has been used for the production in enantiomerically pure form of commercially interesting compounds like naproxen and clopidogrel (Plavix). Finally an STM investigation of the nucleation behavior of a helicene, prepared via a remarkably short and efficient route, on a metal surface is described.

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

PubMed

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 anaesthetic potency, Heyfelder particularly demanded great caution in the application of chloroform. Explicitely he expected an assistant for chloroformizations, whose only duty was to supervise the inhalations and the patient--a forerunner of the modern specialized anaesthesiologist.

Expanding Thorium Hydride Chemistry Through Th²⁺, Including the Synthesis of a Mixed-Valent Th⁴⁺/Th³⁺ Hydride Complex.

PubMed

Langeslay, Ryan R; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2016-03-30

The reactivity of the recently discovered Th(2+) complex [K(18-crown-6)(THF)2][Cp″3Th], 1 [Cp'' = C5H3(SiMe3)2-1,3], with hydrogen reagents has been investigated and found to provide syntheses of new classes of thorium hydride compounds. Complex 1 reacts with [Et3NH][BPh4] to form the terminal Th(4+) hydride complex Cp″3ThH, 2, a reaction that formally involves a net two-electron reduction. Complex 1 also reacts in the solid state and in solution with H2 to form a mixed-valent bimetallic product, [K(18-crown-6)(Et2O)][Cp″2ThH2]2, 3, which was analyzed by X-ray crystallography, electron paramagnetic resonance and optical spectroscopy, and density functional theory. The existence of 3, which formally contains Th(3+) and Th(4+), suggested that KC8 could reduce [(C5Me5)2ThH2]2. In the presence of 18-crown-6, this reaction forms an analogous mixed-valent product formulated as [K(18-crown-6)(THF)][(C5Me5)2ThH2]2, 4. A similar complex with (C5Me4H)(1-) ligands was not obtained, but reaction of (C5Me4H)3Th with H2 in the presence of KC8 and 2.2.2-cryptand at -45 °C produced two monometallic hydride products, namely, (C5Me4H)3ThH, 5, and [K(2.2.2-cryptand)]{(C5Me4H)2[η(1):η(5)-C5Me3H(CH2)]ThH]}, 6. Complex 6 contains a metalated tetramethylcyclopentadienyl dianion, [C5Me3H(CH2)](2-), that binds in a tuck-in mode.

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

PubMed

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.

A calix[4]arene strapped calix[4]pyrrole: an ion-pair receptor displaying three different cesium cation recognition modes.

PubMed

Kim, Sung Kuk; Sessler, Jonathan L; Gross, Dustin E; Lee, Chang-Hee; Kim, Jong Seung; Lynch, Vincent M; Delmau, Laetitia H; Hay, Benjamin P

2010-04-28

An ion-pair receptor, the calix[4]pyrrole-calix[4]arene pseudodimer 2, bearing a strong anion-recognition site but not a weak cation-recognition site, has been synthesized and characterized by standard spectroscopic means and via single-crystal X-ray diffraction analysis. In 10% CD(3)OD in CDCl(3) (v/v), this new receptor binds neither the Cs(+) cation nor the F(-) anion when exposed to these species in the presence of other counterions; however, it forms a stable 1:1 solvent-separated CsF complex when exposed to these two ions in concert with one another in this same solvent mixture. In contrast to what is seen in the case of a previously reported crown ether "strapped" calixarene-calixpyrrole ion-pair receptor 1 (J. Am. Chem. Soc. 2008, 130, 13162-13166), where Cs(+) cation recognition takes place within the crown, in 2.CsF cation recognition takes place within the receptor cavity itself, as inferred from both single-crystal X-ray diffraction analyses and (1)H NMR spectroscopic studies. This binding mode is supported by calculations carried out using the MMFF94 force field model. In 10% CD(3)OD in CDCl(3) (v/v), receptor 2 shows selectivity for CsF over the Cs(+) salts of Cl(-), Br(-), and NO(3)(-) but will bind these other cesium salts in the absence of fluoride, both in solution and in the solid state. In the case of CsCl, an unprecedented 2:2 complex is observed in the solid state that is characterized by two different ion-pair binding modes. One of these consists of a contact ion pair with the cesium cation and chloride anion both being bound within the central binding pocket and in direct contact with one another. The other mode involves a chloride anion bound to the pyrrole NH protons of a calixpyrrole subunit and a cesium cation sandwiched between two cone shaped calix[4]pyrroles originating from separate receptor units. In contrast to what is seen for CsF and CsCl, single-crystal X-ray structural analyses and (1)H NMR spectroscopic studies reveal that receptor 2 forms a 1:1 complex with CsNO(3), with the ions bound in the form of a contact ion pair. Thus, depending on the counteranion, receptor 2 is able to stabilize three different ion-pair binding modes with Cs(+), namely solvent-bridged, contact, and host-separated.

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

Treesearch

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...

α-Diazo oxime ethers for N-heterocycle synthesis.

PubMed

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.

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

PubMed

Babailov, Sergey P

2012-02-06

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

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

PubMed

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.

Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makrlik, Emanuel; Toman, Petr; Vanura, Petr

2013-01-01

From extraction experiments and -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl+ (aq) + 1 Cs+ (org) 1 Tl+ (org) + Cs+ (aq) taking place in the two-phase water phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (Tl+, 1 Cs+) = 1.7 0.1. Further, the extraordinarily high stability constant of the 1 Tl+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log org(1 Tl+) = 13.1 0.2. Finally, by using quantum mechanical DFT calculations, themore » most probable structure of the cationic complex species 1 Tl+ was derived. In the resulting 1 Tl+ complex, the central cation Tl+ 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 receptor 1 via cation interaction.« less

Syntheses, Structures, and Binding Constants of Cyclic Ether and Thioether Adducts of Soluble Cadmium(II) Carboxylates. Intermediates in the Homopolymerization of Oxiranes and Thiiranes and in Carbon Dioxide Coupling Processes.

PubMed

Darensbourg, Donald J.; Niezgoda, Sharon A.; Holtcamp, Matthew W.; Draper, Jennifer D.; Reibenspies, Joseph H.

1997-05-21

A synthetic methodology for the preparation of a large variety of eta(3)-HB(3-Phpz)(3)Cd(acetate) adducts is presented which involves replacement of toluene in the eta(3)-HB(3-Phpz)(3)Cd(acetate) solvate complex by the appropriate cyclic ether or cyclic thioether. In this manner, adducts of THF, dioxane, propylene oxide, cyclohexene oxide, and propylene sulfide were isolated. The solid-state structures of several of these complexes were determined by X-ray crystallography, revealing a six-coordinate complex where the acetate ligand is shown to be fairly symmetrically bonded to the cadmium center. In methylene chloride solution, the cyclic ether or thioether readily dissociates to afford the five-coordinate complex, as demonstrated by (113)Cd NMR. A quantitative assessment of the binding of these base adducts of eta(3)-HB(3-Phpz)(3)Cd(acetate) was determined by measuring the temperature dependence of the equilibrium constants for the five- and six-coordinate derivatives. The presence of one sharp (113)Cd resonance in this equilibrium mixture is indicative of rapid intermolecular exchange between the five- and six-coordinate complexes when compared to the chemical shift differences in these two species ( approximately 6600 Hz at 89 MHz). The order established for ether binding is THF > dioxane > propylene sulfide > cyclohexene oxide >/= propylene oxide, with DeltaH degrees and DeltaS degrees spanning the ranges -27.7 to 24.3 kJ/mol and -89.7 to -94.1 J/(mol K). The epoxide and thioepoxide adducts were shown to serve as models for the initiation step in the copolymerization of epoxides with carbon dioxide catalyzed by metal carboxylates. That is, the carboxylate ligand was shown to ring-open the epoxide or thioepoxide, subsequently affording polyethers or polythioethers with ester end groups. By way of contrast, in the presence of CO(2) and epoxides, this system led to cyclic carbonate production.

A high-spin and durable polyradical: poly(4-diphenylaminium-1,2-phenylenevinylene).

PubMed

Murata, Hidenori; Takahashi, Masahiro; Namba, Kazuaki; Takahashi, Naoki; Nishide, Hiroyuki

2004-02-06

A purely organic, high-spin, and durable polyradical molecule was synthesized: It is based on the non-Kekulé- and non-disjoint design of a pi-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)amino-2-bromostyrene 5 were synthesized and polymerized with a palladium-phosphine catalyst to afford the head-to-tail-linked polyradical precursors (1). Oxidation of 1 with the nitrosonium ion solubilized with a crown ether gave the aminium polyradicals (1(+)()) which were durable (half-life > 1 month) at room temperature in air. A high-spin ground state with an average S = (4.5)/2 for 1a(+) was proved even at room temperature by magnetic susceptibility, magnetization, ESR, and NMR measurements.

Peter J Derrick and the Grand Scale 'Magnificent Mass Machine' mass spectrometer at Warwick.

PubMed

Colburn, A W; Derrick, Peter J; Bowen, Richard D

2017-12-01

The value of the Grand Scale 'Magnificent Mass Machine' mass spectrometer in investigating the reactivity of ions in the gas phase is illustrated by a brief analysis of previously unpublished work on metastable ionised n-pentyl methyl ether, which loses predominantly methanol and an ethyl radical, with very minor contributions for elimination of ethane and water. Expulsion of an ethyl radical is interpreted in terms of isomerisation to ionised 3-pentyl methyl ether, via distonic ions and, possibly, an ion-neutral complex comprising ionised ethylcyclopropane and methanol. This explanation is consistent with the closely similar behaviour of the labelled analogues, C 3 H 7 CH 2 CD 2 OCH 3 +. and C 3 H 7 CD 2 CH 2 OCH 3 +. , and is supported by the greater kinetic energy release associated with loss of ethane from ionised n-propyl methyl ether compared to that starting from directly generated ionised 3-pentyl methyl ether.

Activation of C-O and C-C bonds and formation of novel HAlOH-ether complexes: an EPR study of the reaction of ground-state Al atoms with methylethyl ether and diethyl ether.

PubMed

Brunet, François D; Feola, Julie C; Joly, Helen A

2012-03-15

Reaction mixtures, containing Al atoms and methylethyl ether (MEE) or diethyl ether (DEE) in an adamantane matrix, were prepared with the aid of a metal-atom reactor known as a rotating cryostat. The EPR spectra of the resulting products were recorded from 77-260 K, at 10 K intervals. Al atoms were found to insert into methyl-O, ethyl-O, and C-C bonds to form CH(3)AlOCH(2)CH(3), CH(3)OAlCH(2)CH(3), and CH(3)OCH(2)AlCH(3), respectively, in the case of MEE while DEE produced CH(3)CH(2)AlOCH(2)CH(3) and CH(3)AlCH(2)OCH(2)CH(3), respectively. From the intensity of the transition lines attributed to the Al atom C-O insertion products of MEE, insertion into the methyl-O bond is preferred. The Al hyperfine interaction (hfi) extracted from the EPR spectra of the C-O insertion products was greater than that of the C-C insertion products, that is, 5.4% greater for the DEE system and 7% greater for the MEE system. The increase in Al hfi is thought to arise from the increased electron-withdrawing ability of the substituents bonded to Al. Besides HAlOH, resulting from the reaction of Al atoms with adventitious water, novel mixed HAlOH:MEE and HAlOH:DEE complexes were identified with the aid of isotopic studies involving H(2)(17)O and D(2)O. The Al and H hfi of HAlOH were found to decrease upon complex formation. These findings are consistent with the nuclear hfi calculated using a density functional theory (DFT) method with close agreement between theory and experiment occurring at the B3LYP level using a 6-311+G(2df,p) basis set.

Fusarium algeriense sp. nov., a novel toxigenic crown rot pathogen of durum wheat from Algeria is nested within the Fusarium burgessii species complex

USDA-ARS?s Scientific Manuscript database

A novel crown rot pathogen of wheat discovered during pathogen surveys of Algeria in 2014 and 2015 is formally described here as Fusarium algeriense. Multilocus molecular phylogenetic data resolved the eight isolates of this pathogen as a genealogically exclusive species lineage within the F. burges...

INFLUENCE OF ANESTHESIA ON EXPERIMENTAL NEUROTROPIC VIRUS INFECTIONS

PubMed Central

Sulkin, S. Edward; Zarafonetis, Christine; Goth, Andres

1946-01-01

Anesthesia with diethyl ether significantly alters the course and outcome of experimental infections with the equine encephalomyelitis virus (Eastern or Western type) or with the St. Louis encephalitis virus. No comparable effect is observed in experimental infections produced with rabies or poliomyelitis (Lansing) viruses. The neurotropic virus infections altered by ether anesthesia are those caused by viruses which are destroyed in vitro by this anesthetic, and those infections not affected by ether anesthesia are caused by viruses which apparently are not destroyed by ether in vitro. Another striking difference between these two groups of viruses is their pathogenesis in the animal host; those which are inhibited in vivo by ether anesthesia tend to infect cells of the cortex, basal ganglia, and only occasionally the cervical region of the cord. On the other hand, those which are not inhibited in vivo by ether anesthesia tend to involve cells of the lower central nervous system and in the case of rabies, peripheral nerves. This difference is of considerable importance in view of the fact that anesthetics affect cells of the lower central nervous system only in very high concentrations. It is obvious from the complexity of the problem that no clear-cut statement can be made at this point as to the mechanism of the observed effect of ether anesthesia in reducing the mortality rate in certain of the experimental neurotropic virus infections. Important possibilities include a direct specific effect of diethyl ether upon the virus and a less direct effect of the anesthetic upon the virus through its alteration of the metabolism of the host cell. PMID:19871570

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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 (< 3%) and near infrared (< 10%) spectral ranges. These differences between model simulations and measurements were significantly correlated to TLS-derived tree crown complexity metrics. The specific implications of internal crown complexity on estimating leaf chlorophyll concentration, a pertinent physiological health indicator, is highlighted. This research demonstrates that TLS systems can potentially be the new observational tool and benchmark for precise characterization of vegetation architecture for synergy with 3D radiative transfer models for improved operational management of agricultural crops.

Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1).

PubMed

Wolf, Robert; Ehlers, Andreas W; Khusniyarov, Marat M; Hartl, František; de Bruin, Bas; Long, Gary J; Grandjean, Fernande; Schappacher, Falko M; Pöttgen, Rainer; Slootweg, J Chris; Lutz, Martin; Spek, Anthony L; Lammertsma, Koop

2010-12-27

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and Mössbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed.

Analysis of the gingival biotype based on the measurement of the dentopapillary complex

PubMed Central

Malhotra, Ranjan; Grover, Vishakha; Bhardwaj, Arvind; Mohindra, Kanika

2014-01-01

Background: The gingival morphology of the maxillary anterior region plays an important role in determining the final esthetic outcome. Knowledge of the periodontal biotype is of fundamental importance because the anatomical characteristics of the periodontium, such as gingival thickness, gingival width and alveolar bone morphology, will determine periodontium behavior when submitted to physical, chemical, or bacterial injury or during periodontal or implant surgical procedures and orthodontic treatment. Materials and Methods: 50 subjects with healthy periodontal tissues with no loss of attachment and (b) presence of all anterior teeth in both upper and lower jaw were selected. On clinical examination gingival thickness was recorded based on the transparency of periodontal probe. Following parameters are recorded from dental cast, i.e., crown length, crown width, papillary length (PL) and papillary width. Results: There was highly significant correlation between gingival biotype and crown length and area of papilla with P value −0.002 and 0.013 respectively. Significant correlation was found between area of crown and PL with P value −0.013 and 0.016. The results of discriminant function analysis showed that average crown length was the best single determinant of biotype and area of papilla was the next best choice. Conclusion: Within the limits of the current investigation, the existence and correlation of different gingival biotypes and dentopapillary complex dimension has been confirmed. These findings can be utilized as objective guidelines for determining the biotype and response of gingiva to many dental operative procedures. PMID:24744543

Diastereoselective sp2-sp3 coupling of sugar enol ethers with unactivated cycloalkenes: new entries to C-branched sugars.

PubMed

Hussain, Nazar; Tatina, Madhu Babu; Rasool, Faheem; Mukherjee, Debaraj

2016-10-25

Sugar enol ethers undergo efficient coupling at C-2 with unactivated cycloalkenes under a low Pd loading affording allylic substitution products. High diastereoselectivity was observed at the allylic centre with sterically hindered substrates. Generation of a π-allyl complex by the Pd(ii) catalyst via cleavage of the allylic C-H bond of the cycloalkene may be responsible for the formation of sp 2 -sp 3 coupling products.

The Design, Synthesis and Screening of Potential Pyridinium Oxime Prodrugs.

DTIC Science & Technology

1985-07-31

copper sulfate pentahydrate , and 15 g (87 mol) of the mixture of bromo- picolines 13c and 131. The combined reactions produced 27 g (96%) of a brown...extracted with ethyl ether. The ether extracts were washed with brine, dried with sodium sulfate , filtered and flashed. The residue was then purified by...stirring to the reaction mix. The addition was exothermic as the copper complexes decomposed. The cooled mixture was extracted with several 20 ml

Conformation and Complexation of Tannins: NMR Spectra and Molecular Search Modeling of Flavan-3-ols

Treesearch

Richard W. Hemingway; Fred L. Tohiason; G. Wayne McGraw; Jan P. Steynberg

1996-01-01

Studies offlavan-3-01sin their biologically significant phenolic form show that both H-6 and C-6 resonances are downfield from H-8 and C-8. Therefore, assignments for the H atoms of the A-ring are inverse to those commonly reported. By contrast, in the methyl ether and methyl ether acetate derivatives, both H-8 and C-8 are downfield from H-6 and C-6 and assignments...

Effect of ionophores on the rate of intramolecular cation exchange in durosemiquinone ion pairs

NASA Technical Reports Server (NTRS)

Eastman, M. P.; Bruno, G. V.; Mcguyer, C. A.; Gutierrez, A. R.; Shannon, J. M.

1979-01-01

The effects of the ionophores 15-crown-5 (15C5), 18-crown-6 (18C6), dibenzo-18-crown-6 (DBC) and cryptand 222 (C222) on intramolecular cation exchange in ion pairs of the sodium salt of the durosemiquinone anion in benzene solution are investigated. Electron paramagnetic resonance spectra of the 18C6 and 15C5 complexes with durosemiquinone reduced by contact with a sodium mirror show an alternating line width which indicates that the sodium ion is being exchanged between equivalent sites near the oxygens of the semiquinone with activation energies of 8.7 and 6.0 kcal/mole and Arrhenius preexponential factors of 9 x 10 to the 12th/sec and 10 to the 12th/sec, respectively. Spectra obtained for the DBC complexes show no evidence of exchange, while those of C222 indicate rapid exchange. It is also noted that the hyperfine splitting constants measured do not change over the 50-K temperature interval studied.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Piezoresistive microcantilever based lab-on-a-chip system for detection of macronutrients in the soil

NASA Astrophysics Data System (ADS)

Patkar, Rajul S.; Ashwin, Mamta; Rao, V. Ramgopal

2017-12-01

Monitoring of soil nutrients is very important in precision agriculture. In this paper, we have demonstrated a micro electro mechanical system based lab-on-a-chip system for detection of various soil macronutrients which are available in ionic form K+, NO3-, and H2PO4-. These sensors are highly sensitive piezoresistive silicon microcantilevers coated with a polymer matrix containing methyltridodecylammonium nitrate ionophore/ nitrate ionophore VI for nitrate sensing, 18-crown-6 ether for potassium sensing and Tributyltin chloride for phosphate detection. A complete lab-on-a-chip system integrating a highly sensitive current excited Wheatstone's bridge based portable electronic setup along with arrays of microcantilever devices mounted on a printed circuit board with a liquid flow cell for on the site experimentation for soil test has been demonstrated.

Matrix isolation studies of the interactions of BF3 with water and substituted diethyl ethers. Chemical ionization mass spectrometric determination of the proton affinity of (CF3CH2)2O

NASA Technical Reports Server (NTRS)

Ball, David W.; Zehe, Michael J.

1993-01-01

BF3 was co-condensed with H2O, D2O, (C2H5)2O, (CF3CH2)2O, and (C2F5)2O in excess argon at 15 K. Infrared spectra of BF3/water isolated in solid argon provided a more complete analysis of the BF3--H2O complex than previously published. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis (2,2,2-trifluorodiethyl) ether, and no observable interaction with perfluorodiethyl ether. Thus, the ether data indicate a clear trend between strength of interaction with BF3 and the degree of F substitution. To support and explain the emerging relationship between interaction strength and the basicity of the oxygen-containing molecule, the proton affinity of (CF3CH2)2O was measured using chemical ionization mass spectrometry. The implications of the results for lubricant/metal oxide surface interactions are discussed.

Application of annular centrifugal contactors in the hot test of the improved total partitioning process for high level liquid waste.

PubMed

Duan, Wuhua; Chen, Jing; Wang, Jianchen; Wang, Shuwei; Feng, Xiaogui; Wang, Xinghai; Li, Shaowei; Xu, Chao

2014-08-15

High level liquid waste (HLLW) produced from the reprocessing of the spent nuclear fuel still contains moderate amounts of uranium, transuranium (TRU) actinides, (90)Sr, (137)Cs, etc., and thus constitutes a permanent hazard to the environment. The partitioning and transmutation (P&T) strategy has increasingly attracted interest for the safe treatment and disposal of HLLW, in which the partitioning of HLLW is one of the critical technical issues. An improved total partitioning process, including a TRPO (tri-alkylphosphine oxide) process for the removal of actinides, a CESE (crown ether strontium extraction) process for the removal of Sr, and a CECE (calixcrown ether cesium extraction) process for the removal of Cs, has been developed to treat Chinese HLLW. A 160-hour hot test of the improved total partitioning process was carried out using 72-stage 10-mm-dia annular centrifugal contactors (ACCs) and genuine HLLW. The hot test results showed that the average DFs of total α activity, Sr and Cs were 3.57 × 10(3), 2.25 × 10(4) and 1.68 × 10(4) after the hot test reached equilibrium, respectively. During the hot test, 72-stage 10-mm-dia ACCs worked stable, continuously with no stage failing or interruption of the operation. Copyright © 2014 Elsevier B.V. All rights reserved.

Anti-fertility effects of different fractions of Anethum graveolens L. extracts on female rats.

PubMed

Malihezaman, Monsefi; Mojaba, Masoudi; Elham, Hosseini; Farnaz, Gramifar; Ramin, Miri

2012-01-01

Our previous studies showed the effects of aqueous and ethanol extracts of Anethum graveolens L. (dill) on female infertility. In the present study we investigated whether different fractions of this herb extract can cause infertility in rats. Female rats were divided into the control groups, the groups receiving either a low (0.5 g/kg)) or a high dose (5g/kg) of water, N-butanol, chloroform and ether fractions of the aqueous plant extract, and the groups receiving either a low (0.045 g/kg) or a high dose (0.45 g/kg) of the same fractions of ethanol extract. The mentioned doses were gavaged in 1mL for 10 days. Vaginal smears were prepared daily. Estradiol and progesterone levels were measured. The left oviduct and ovary were removed, their tissue subsequently being prepared in form of histology slides and stained using haematoxylin-eosin and Masson's trichrome. Female rats assigned to each group were mated with males; after that, crown-rump lengths and weights of newborn rats were measured. Results showed that each fraction produced some changes such as hormonal level reduction (chloroform fraction), diestrus phase prolongation and infertility (water fraction), and increase in pregnancy duration (chloroform and ether fractions). We concluded that each fraction comprises only some of the mentioned components and therefore recommended the usage of crude extract, especially the aqueous one, in case infertility aims to be induced.

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

PubMed

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.

Hydration Differences Explain the Large Variations in the Complexation Thermodynamics of Modified γ-Cyclodextrins with Bile Salts.

PubMed

Køhler, Jonatan; Schönbeck, Christian; Westh, Peter; Holm, René

2016-01-28

The structure and thermodynamics of inclusion complexes of seven different γ-cyclodextrins (γCDs) and three biologically relevant bile salts (BS) were investigated in the present study. Natural γCD and six modified γCDs [two methyl-γCDs, one sulfobutyl ether-γCD (SBEγCD), and three 2-hydroxypropyl-γCDs (HPγCD)] and their complexes with BS were investigated by isothermal titration calorimetry, NMR, and molecular dynamics simulations. With the exception of the fully methylated γCD, which did not bind the BSs investigated, all of the γCDs formed 1:1 complexes with the BS, and the structures were similar to those with natural γCD; i.e., the modifications of the γCD had limited structural impact on the formation of complexes. Isothermal titration calorimetry was carried out over in the temperature interval 5-55 °C to enable the calculation of the stability constant (K) and the thermodynamic parameters enthalpy (ΔH°), entropy (ΔS°), and heat capacity (ΔCp°). The stability constants decreased with an increased degree of substitution (DS), with methyl substituents having a lower effect on the stability constant than the sulfobutyl ether and hydroxypropyl substituents on the stability constants. Enthalpy-entropy compensation was observed, since both enthalpy and entropy increased with the degree of substitution, which may reflect dehydration of the hydrophobic surface on both CD and BS. Calculations based on ΔCp° data suggested that each of the substituents dehydrated 10-20 (hydroxypropyl), 22-33 (sulfobutyl ether), and 10-15 Å(2) (methyl) of the BS surface area, in reasonable agreement with estimates from the molecular dynamics simulations. Combined with earlier investigations on modified βCDs, these results indicate general trends of the substituents on the thermodynamics of complex formation.

Directional radiative transfer by SCOPE, SLC and DART using laser scan derived structural forest parameters

NASA Astrophysics Data System (ADS)

Timmermans, Joris; Gastellu-Etchegorry, Jean Philippe; van der Tol, Christiaan; Verhoef, Wout; Vekerdy, Zoltan; Su, Zhongbo

2017-04-01

Accurate estimation of the radiative transfer (RT) over vegetation is the corner stone of agricultural and hydrological remote sensing applications. Present remote sensing sensors mostly use traditional optical, thermal and microwave observations. However with these traditional observations characterization of the light efficiency and photosynthetic rate can only be accomplished indirectly. A promising new method of observing these processes is by using the fluorescent emitted radiation. This approach was recently highlighted due to the selection of the FLEX sensor as a future Earth Explorer by the European Space agency (ESA). Several modelling activities have been undertaken to better understand the technical feasibilities of this sensor. Within these studies, the SCOPE model has been chosen as the baseline algorithm. This model combines a detailed RT description of the canopy, using a discrete version of the SAIL model, with a description of photosynthetic processes (by use of the Farquhar/Ball-Berry model). Consequently, this model is capable of simulating simultaneously the biophysical processes and jointly the fluorescent, optical and thermal RT. The SAIL model however is a 1D RT model and consequently provides higher uncertainties with increasing vegetation structures. The main objective of this research is to investigate the limitations of the RT model component of the SCOPE model over complex canopies. In particular the aim of this research is to evaluate the validity for increasingly structural complex canopies', on the bidirectional reflectance distribution functions (BRDF) of these canopies. This was accomplished by evaluating the simulated outgoing radiation from SCOPE/SAIL against simulations of the DART 3D RT model. In total nine different scenarios were simulated with the DART RTM with increasing structural complexity, ranging from the simple 'Plot' scenario to the highly complex 'Multiple Crown' scenario. The canopy parameters are retrieved from a terrestrial laser scan of the Speulderbos in the Netherlands. The comparison between DART and SCOPE/SLC models showed a good match for the simple scenarios. Calculated rMSDs showed lower than 7.5% errors for crown coverage values lower than 0.87, with the Near-Hotspot viewing angles found to be the largest contributor to this deviation. For more complex scenarios (using Multiple Crowns), the comparison between SCOPE and DART showed mixed results. Good results were obtained for crown coverage values of 0.93, with rMSD (6.77% and 5.96%), lower than the defined threshold value, except near hotspot. For scenarios with crown coverages lower than 0.93 the rMSD were too large to validate the use of SCOPE model. When considering the Soil Leaf Canopy (SLC) model, an improved version of SAIL that considers the canopy clumping, better results were obtained for these complex scenarios, with good agreement for medium crown coverage values (0.93 and 0.87) with rMSD (6.33% and 5.99; 6.66% and 7.12%). This indicates that the radiative transfer model within SCOPE might be upgraded in the future.

The perio-esthetic-restorative approach for anterior rehabilitation

PubMed Central

Tomar, Nitin; Bansal, Tushika; Bhandari, Marisha; Sharma, Anamika

2013-01-01

Ensuring clinical success begins with a careful discussion of treatment planning, comprehensively covering all variables in simple to complex cases. Procedures including the crown lengthening surgery, furcation treatment and mucogingival therapy and tooth restoration are essential treatment regimens requiring multifaceted expertise. The interplay of periodontics and restorative dentistry is present at many fronts including the response of the gingival tissue to the restorative preparations. Dental restorations and periodontal health are inseparably interrelated. The adaptation of the margins, the contours of the restoration, the proximal relationships and the surface smoothness have a critical biological impact on the gingiva and the supporting periodontal tissues. The different surgical procedures used for crown lengthening are gingivectomy/gingivoplasty, apically positioned flap with or without osseous resection and orthodontic extrusion. The paper presents crown lengthening of severely mutilated teeth to increase the clinical crown height for adequate restoration. PMID:24174740

Explosive avian radiations and multi-directional dispersal across Wallacea: evidence from the Campephagidae and other Crown Corvida (Aves).

PubMed

Jønsson, Knud A; Irestedt, Martin; Fuchs, Jérôme; Ericson, Per G P; Christidis, Les; Bowie, Rauri C K; Norman, Janette A; Pasquet, Eric; Fjeldså, Jon

2008-04-01

The systematic relationships among avian families within Crown Corvida have been poorly studied so far and as such been of limited use for biogeographic interpretations. The group has its origin in Australia and is thought to have colonized Africa and the New World via Asia beginning some 35 Mya when terranes of Australian origin approached Asian landmasses. Recent detailed tectonic mapping of the origin of land masses in the region around Wallace's line have revealed a particularly complex movement of terranes over the last 20-30 Myr. Thus the biogeographic dispersal pattern of Crown Corvida is a particularly exciting case for linking vicariance and dispersal events with Earth history. Here we examine phylogenetic affinities among 72 taxa covering a broad range of genera in the basal radiations within Crown Corvida with an emphasis on Campephagidae and Pachycephalidae. Bayesian analyses of nuclear DNA sequence data identified the family Campephagidae as monophyletic but the large genus Coracina is not. Within the family Pachycephalidae the genera Pachycephala and Colluricincla are paraphyletic with respect to each other. The resulting phylogeny suggests that patterns of dispersal across Wallace's line are complex and began at least 25 Mya. We find evidence of explosive radiations and multi-directional dispersal within the last 10 Myr, and three independent long distance ocean dispersal events between Wallacea and Africa at 10-15 Mya. Furthermore, the study reveals that in the Campephagidae a complex series of dispersal events rather than vicariance is the most likely explanation for the current biogeographic pattern in the region.

Tandem Carbocupration/Oxygenation of Terminal Alkynes

PubMed Central

Zhang, Donghui; Ready, Joseph M.

2008-01-01

A direct and general synthesis of α-branched aldehydes and their enol derivatives is described. Carbocupration of terminal alkynes and subsequent oxygenation with lithium tert-butyl peroxide generates a metallo-enolate. Trapping with various electrophiles provides α-branched aldehydes or stereo-defined trisubstituted enol esters or silyl ethers. The tandem carbocupration/oxygenation tolerates alkyl and silyl ethers, esters and tertiary amines. The reaction is effective with organocopper complexes derived from primary, secondary and tertiary Grignard reagents and from n-butyllithium. PMID:16321021

Sorption reaction mechanism of some hazardous radionuclides from mixed waste by impregnated crown ether onto polymeric resin.

PubMed

Shehata, F A; Attallah, M F; Borai, E H; Hilal, M A; Abo-Aly, M M

2010-02-01

A novel impregnated polymeric resin was practically tested as adsorbent material for removal of some hazardous radionuclides from radioactive liquid waste. The applicability for the treatment of low-level liquid radioactive waste was investigated. The material was prepared by loading 4,4'(5')di-t-butylbenzo 18 crown 6 (DtBB18C6) onto poly(acrylamide-acrylic acid-acrylonitril)-N, N'-methylenediacrylamide (P(AM-AA-AN)-DAM). The removal of (134)Cs, (60)Co, (65)Zn , and ((152+154))Eu onto P(AM-AA-AN)-DAM/DtBB18C6 was investigated using a batch equilibrium technique with respect to the pH, contact time, and temperature. Kinetic models are used to determine the rate of sorption and to investigate the mechanism of sorption process. Five kinetics models, pseudo-first-order, pseudo-second-order, intra-particle diffusion, homogeneous particle diffusion (HPDM), and Elovich models, were used to investigate the sorption process. The obtained results of kinetic models predicted that, pseudo-second-order is applicable; the sorption is controlled by particle diffusion mechanism and the process is chemisorption. The obtained values of thermodynamics parameters, DeltaH degrees , DeltaS degrees , and DeltaG degrees indicated that the endothermic nature, increased randomness at the solid/solution interface and the spontaneous nature of the sorption processes. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Pressure-assisted introduction of urine samples into a short capillary for electrophoretic separation with contactless conductivity and UV spectrometry detection.

PubMed

Makrlíková, Anna; Opekar, František; Tůma, Petr

2015-08-01

A computer-controlled hydrodynamic sample introduction method has been proposed for short-capillary electrophoresis. In the method, the BGE flushes sample from the loop of a six-way sampling valve and is carried to the injection end of the capillary. A short pressure impulse is generated in the electrolyte stream at the time when the sample zone is at the capillary, leading to injection of the sample into the capillary. Then the electrolyte flow is stopped and the separation voltage is turned on. This way of sample introduction does not involve movement of the capillary and both of its ends remain constantly in the solution during both sample injection and separation. The amount of sample introduced to the capillary is controlled by the duration of the pressure pulse. The new sample introduction method was tested in the determination of ammonia, creatinine, uric acid, and hippuric acid in human urine. The determination was performed in a capillary with an overall length of 10.5 cm, in two BGEs with compositions 50 mM MES + 5 mM NaOH (pH 5.1) and 1 M acetic acid + 1.5 mM crown ether 18-crown-6 (pH 2.4). A dual contactless conductivity/UV spectrometric detector was used for the detection. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of ammonium in wastewaters by capillary electrophoresis on a column-coupling chip with conductivity detection.

PubMed

Luc, Milan; Kruk, Pavol; Masár, Marián

2011-07-01

Analytical potentialities of a chip-based CE in determination of ammonium in wastewaters were investigated. CZE with the electric field and/or ITP sample stacking was performed on a column-coupling (CC) chip with integrated conductivity detectors. Acetate background electrolytes (pH ∼3) including 18-crown-6-ether (18-crown-6) and tartaric acid were developed to reach rapid (in 7-8 min) CZE and ITP-CZE resolutions of ammonium from other cations (sodium, potassium, calcium and magnesium) present in wastewater samples. Under preferred working conditions (suppressed hydrodynamic flow (HDF) and EOF on the column-coupling chip), both the employed methods did provide very good repeatabilities of the migration (RSD of 0.2-0.8% for the migration time) and quantitative (RSD of 0.3-4.9% for the peak area) parameters in the model and wastewater samples. Using a 900-nL sample injection volume, LOD for ammonium were obtained at 20 and 40 μg/L concentrations in CZE and ITP-CZE separations, respectively. Very good agreements of the CZE and ITP-CZE determinations of ammonium in six untreated wastewater samples (only filtration and dilution) with the results obtained by a reference spectrometric method indicate a very good accuracy of both the CE methods presented. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assembly and Properties of Heterobimetallic CoII/III/CaII Complexes with Aquo and Hydroxo Ligands

PubMed Central

Lacy, David C.; Park, Young Jun; Ziller, Joseph W.; Yano, Junko; Borovik, A. S.

2012-01-01

The use of water as a reagent in redox-driven reactions is advantageous because it is abundant and environmentally compatible. The conversion of water to dioxygen in photosynthesis illustrates one example, in which a redox-inactive CaII ion and four manganese ions are required for function. In this report we describe the stepwise formation of two new heterobimetallic complexes containing CoII/III and CaII ions, and either hydroxo or aquo ligands. The preparation of a 4-coordinate CoII synthon was achieved with the tripodal ligand, N,N′,N″-[2,2′,2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido, [MST]3−. Water binds to [CoIIMST]− to form the 5-coordinate [CoIIMST(OH2)]− complex that was used to prepare the CoII/CaII complex [CoIIMST(μ-OH2)CaII⊂15-crown-5(OH2)]+ ([CoII(μ-OH2)CaIIOH2]+). [CoII(μ-OH2)CaOH2]+ contained two aquo ligands, one bonded to the CaII ion and one bridging between the two metal ions and thus represents an unusual example of a heterobimetallic complex containing 2 aquo ligands spanning different metal ions. Both aquo ligands formed intramolecular hydrogen bonds with the [MST]3− ligand. [CoIIMST(OH2)]− was oxidized to form [CoIIIMST(OH2)] that was further converted to [CoIIIMST(μ-OH)CaII⊂15-crown-5]+ ([CoIII(μ-OH)CaII]+) in the presence of base and CaIIOTf2/15-crown-5. [CoIII(μ-OH)CaII]+ was also synthesized from the oxidation of [CoIIMST]− with PhIO in the presence of CaIIOTf2/15-crown-5. Allowing [CoIII(μ-OH)CaII]+ to react with diphenylhydrazine afforded [CoII(μ-OH2)CaIIOH2]+ and azobenzene. Additionally, the characterization of [CoIII(μ-OH)CaII]+ provides another formulation for the previously reported CoIV–oxo complex, [(TMG3tren)CoIV(μ-O)ScIII(OTf)3]2+ to one that instead could contain a CoIII–OH unit. PMID:22998407

Interaction of single-walled carbon nanotubes with poly(propyl ether imine) dendrimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayamurugan, G.; Rajesh, Y. B. R. D.; Jayaraman, N.

2011-03-14

We study the complexation of nontoxic, native poly(propyl ether imine) dendrimers with single-walled carbon nanotubes (SWNTs). The interaction was monitored by measuring the quenching of inherent fluorescence of the dendrimer. The dendrimer-nanotube binding also resulted in the increased electrical resistance of the hole doped SWNT, due to charge-transfer interaction between dendrimer and nanotube. This charge-transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. We also report the effect of acidic and neutral pH conditions on the binding affinities. Experimental studies were supplemented by all atom molecular dynamics simulations to provide amore » microscopic picture of the dendrimer-nanotube complex. The complexation was achieved through charge transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen, and n-propyl moieties of the dendrimer.« less

Competitive cesium-133 NMR spectroscopic study of complexation of different metal ions with dibenzo-21-crown-7 in acetonitrile-dimethylsulfoxide and nitromethane-dimethylsulfoxide mixtures.

PubMed

Sahmsipur, Mojtaba; Dastjerdi, Leila Shafiee; Alizadeh, Nader; Bijanzadeh, Hamid Reza

2008-04-01

(133)Cs NMR spectroscopy was used to determine the stoichiometry and stability of the Cs(+) ion complex with dibenzo-21-crown-7 (DB21C7) in acetonitrile-dimethylsulfoxide (96.5:3.5, w/w) and nitromethane-dimethylsulfoxide (96.5:3.5, w/w) mixtures. A competitive (133)Cs NMR technique was also employed to probe the complexation of Na(+), K(+), Rb(+), Ag(+), Tl(+), NH(4)(+), Mg(2+), Ba(2+), Hg(2+), Pb(2+) and UO(2)(2+) ions with DB21C7 in the same solvent systems. All the resulting 1:1 complexes in nitromethane-dimethylsulfoxide were more stable than those in acetonitrile-dimethylsulfoxide solution. In both solvent systems, the stability of the resulting complexes was found to vary in the order Rb(+)>K(+) approximately Ba(2+)>Tl(+)>Cs(+)>NH(4)(+) approximately Pb(2+)>Ag(+)>UO(2)(2+)>Hg(2+)>Mg(2+)>Na(+).

Synthetic bioactive novel ether based Schiff bases and their copper(II) complexes

NASA Astrophysics Data System (ADS)

Shabbir, Muhammad; Akhter, Zareen; Ismail, Hammad; Mirza, Bushra

2017-10-01

Novel ether based Schiff bases (HL1- HL4) were synthesized from 5-chloro-2-hydroxy benzaldehyde and primary amines (1-amino-4-phenoxybenzene, 4-(4-aminophenyloxy) biphenyl, 1-(4-aminophenoxy) naphthalene and 2-(4-aminophenoxy) naphthalene). From these Schiff bases copper(II) complexes (Cu(L1)2-Cu(L4)2)) were synthesized and characterized by elemental analysis and spectroscopic (FTIR, NMR) techniques. The synthesized Schiff bases and copper(II) complexes were further assessed for various biological studies. In brine shrimp assay the copper(II) complexes revealed 4-fold higher activity (LD50 3.8 μg/ml) as compared with simple ligands (LD50 12.4 μg/ml). Similar findings were observed in potato disc antitumor assay with higher activities for copper(II) complexes (IC50 range 20.4-24.1 μg/ml) than ligands (IC50 range 40.5-48.3 μg/ml). DPPH assay was performed to determine the antioxidant potential of the compounds. Significant antioxidant activity was shown by the copper(II) complexes whereas simple ligands have shown no activity. In DNA protection assay significant protection behavior was exhibited by simple ligand molecules while copper(II) complexes showed neutral behavior (neither protective nor damaging).

Improvement of electrochemical performances of sulfonated poly(arylene ether sulfone) via incorporation of sulfonated poly(arylene ether benzimidazole)

NASA Astrophysics Data System (ADS)

Hong, Young Taik; Lee, Chang Hyun; Park, Hyung Su; Min, Kyung A.; Kim, Hyung Joong; Nam, Sang Yong; Lee, Young Moo

In the present study, modified acid-base blend membranes were fabricated via incorporation of sulfonated poly(arylene ether benzimidazole) (SPAEBI) into sulfonated poly(arylene ether sulfone) (SPAES). These membranes had excellent methanol-barrier properties in addition to an ability to compensate for the loss of proton conductivity that typically occurs in general acid-base blend system. To fabricate the membranes, SPAEBIs, which served as amphiphilic polymers with different degrees of sulfonation (0-50 mol%), were synthesized by polycondensation and added to SPAES. It resulted in the formation of acid-amphiphilic complexes such as [PAES-SO 3] - +[H-SPAEBI] through the ionic crosslinking, which prevented SO 3H groups in the complex from transporting free protons in an aqueous medium, contributing to a reduction of ion exchange capacity values and water uptake in the blend membranes, and leading to lower methanol permeability in a water-methanol mixture. Unfortunately, the ionic bonding formation was accompanied by a decrease of bound water content and proton conductivity, although the latter problem was solved to some extent by the incorporation of additional SO 3H groups in SPAEBI. In the SPAES-SPAEBI blend membranes, enhancement of proton conductivity and methanol-barrier property was prominent at temperatures over 90 °C. The direct methanol fuel cell (DMFC) performance, which was based on SPAES-SPAEBI-50-5, was 1.2 times higher than that of Nafion ® 117 under the same operating condition.

Mode of Action Studies on Nitrodiphenyl Ether Herbicides

PubMed Central

Bowyer, John R.; Smith, Beverly J.; Camilleri, Patrick; Lee, Susan A.

1987-01-01

5-[2-Chloro-4-(trifluoromethyl)phenoxy]-2-nitroacetophenone oxime-o-(acetic acid, methyl ester) (DPEI), is a potent nitrodiphenyl ether herbicide which causes rapid leaf wilting, membrane lipid peroxidation, and chlorophyll destruction in a process which is both light- and O2-dependent. These effects resemble those of other nitrodiphenyl ether herbicides. Unlike paraquat, the herbicidal effects of DPEI are only slightly reduced by pretreatment with the photosynthetic electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea. DPEI is a weak inhibitor of photosynthetic electron transport (I50 15 micromolar for water to paraquat) in vitro, with at least one site of action at the cytochrome b6f complex. Ultrastructural studies and measurements of ethane formation resulting from lipid peroxidation indicate that mutants of barley lacking photosystem I (PSI) (viridis-zb63) or photosystem II (viridis-zd69) are resistant to paraquat but susceptible to DPEI. The results indicate that electron transfer through both photosystems is not essential for the toxic effects of nitrodiphenyl ether herbicides. Furthermore, the results show that neither cyclic electron transport around PSI, nor the diversion of electrons from PSI to O2 when NADPH consumption is blocked are essential for the phytotoxicity of nitrodiphenyl ether herbicides. Images Fig. 2 Fig. 3 Fig. 4 PMID:16665297

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

PubMed

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.

Platinum(0)-mediated C-O bond activation of ethers via an SN2 mechanism.

PubMed

Ortuño, Manuel A; Jasim, Nasarella A; Whitwood, Adrian C; Lledós, Agustí; Perutz, Robin N

2016-11-29

A computational study of the C(methyl)-O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp 3 ) 2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an S N 2 mechanism. Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(ii) product trans-[PtMe(OAr F )(PCyp 3 ) 2 ]. Structure-reactivity correlations are fully consistent with this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy 3 ) 2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η 3 -allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy 3 ) 2 (η 3 -allyl)][OC 5 NF 4 ]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

Extraction of cesium, strontium and the platinium group metals from acidic high activity nuclear waste using a Purex process compatible organic extractant. Final report, December 15, 1980-August 15, 1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, M.W. Jr.; Van Brunt, V.

1984-09-14

Purex process compatible organic systems which selectively and reversibly extract cesium, strontium, and palladium from synthetic mixed fission product solutions containing 3M HNO/sub 3/ have been developed. This advance makes the development of continuous solvent extraction processes for their recovery more likely. The most favorable cesium and strontium complexing solutions have been tested for radiation stability to 10/sup 7/ rad using a 0.4 x 10/sup 7/ rad/h /sup 60/Co source. The distribution coefficients dropped somewhat but remained above unity. For cesium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % kerosenemore » containing 0.05m Bis 4,4',(5')(1-hydroxy 2-ethylhexyl)-benzo 18-crown-6 (Crown XVII). The NNS is a sulfonic acid cation exchanger. With an aqueous phase containing 0.006M Cs/sup +1/ in contact with an equal volume of extractant the D org/aq = 1.6 at a temperature of 25 to 35/sup 0/C. For strontium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % Kerosene containing 0.02M Bis 4,4'(5') (1-hydroxyheptyl)cyclohexo 18-crown-6 (Crown XVI). With an aqueous phase containing 0.003M Sr/sup +2/ in contact with an equal volume of extractant the D org/aq = 1.98 at a temperature of 25 to 35/sup 0/C. For palladium the complexing organic solution consisted of a ratio of TBP/kerosene of 0.667 containing 0.3M Alamine 336 which is a tertiary amine anion exchanger. With an aqueous phase containing 0.0045M Pd/sup +/ in contact with an equal volume of extractant the D org/aq = 1.95 at a temperature of 25 to 35/sup 0/C.« less

Crystal structure of (18-crown-6)potassium(I) [(1,2,3,4,5-η)-cyclo-hepta-dien-yl][(1,2,3-η)-cyclo-hepta-trien-yl]cobalt(I).

PubMed

Brennessel, William W; Ellis, John E

2015-03-01

The reaction of bis-(anthracene)cobaltate(-I) with excess cyclo-hepta-triene, C7H8, resulted in a new 18-electron cobaltate containing two different seven-membered ring ligands, based on single-crystal X-ray diffraction. The asymmetric unit of this structure contains two independent cation-anion pairs of the title complex, [K(18-crown-6)][Co(η(3)-C7H7)(η(5)-C7H9)], where 18-crown-6 stands for 1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane (C12H24O6), in general positions and well separated. Each (18-crown-6)potassium cation is in contact with the η(3)-coordinating ligand of one cobaltate complex. Each η(3)-coordinating ligand behaves as an allylic anion whose exo-diene moiety is bent away from the allylic plane, and thus is not involved directly in the bonding. The metal-coordinating portions of the anionic η(5) ligands are planar and one of these ligands is modeled as disordered over two positions, with occupancy ratio 0.699 (5):0.301 (5), such that one orientation is rotated by one carbon atom with respect to the other. The diffraction intensities were integrated according to non-merohedral twin law [-1 0 0/0 -1 0/0.064 0 1], a 180° rotation about reciprocal lattice axis [001], and the masses of the twin domains refined to equal amounts. As both ligands are formally coordinated as anions, the cobalt atom is best considered to be Co(I). This compound is of inter-est as the first to possess cyclo-hepta-trienyl and cyclo-hepta-dienyl ligands in an anionic metal complex.

Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makrlik, Emanuel; Toman, Petr; Vanura, Petr

2013-01-01

From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complexmore » species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.« less

Recent Advances in Macrocyclic Fluorescent Probes for Ion Sensing.

PubMed

Wong, Joseph K-H; Todd, Matthew H; Rutledge, Peter J

2017-01-25

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

Method for separating metal chelates from other materials based on solubilities in supercritical fluids

DOEpatents

Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

2001-01-01

A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

Reversible Modulation of DNA-Based Hydrogel Shapes by Internal Stress Interactions.

PubMed

Hu, Yuwei; Kahn, Jason S; Guo, Weiwei; Huang, Fujian; Fadeev, Michael; Harries, Daniel; Willner, Itamar

2016-12-14

We present the assembly of asymmetric two-layer hybrid DNA-based hydrogels revealing stimuli-triggered reversibly modulated shape transitions. Asymmetric, linear hydrogels that include layer-selective switchable stimuli-responsive elements that control the hydrogel stiffness are designed. Trigger-induced stress in one of the layers results in the bending of the linear hybrid structure, thereby minimizing the elastic free energy of the systems. The removal of the stress by a counter-trigger restores the original linear bilayer hydrogel. The stiffness of the DNA hydrogel layers is controlled by thermal, pH (i-motif), K + ion/crown ether (G-quadruplexes), chemical (pH-doped polyaniline), or biocatalytic (glucose oxidase/urease) triggers. A theoretical model relating the experimental bending radius of curvatures of the hydrogels with the Young's moduli and geometrical parameters of the hydrogels is provided. Promising applications of shape-regulated stimuli-responsive asymmetric hydrogels include their use as valves, actuators, sensors, and drug delivery devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Custelcean, Radu; Bartsch, Richard A.

Two series of novel mono-ionizable calix[4]arene-benzocrown-6 ligands in 1,3-alternate conformations are synthesized. In one series, the proton-ionizable group (PIG) is attached to the para position of one aromatic ring in the calixarene framework, thereby positioning it over the polyether ring cavity. In the other series, the PIG is a substituent on the benzo group in the polyether ring. This orients the PIG away from the crown ether cavity. In addition to carboxylic acid functions, the PIGs include N-(X)sulfonyl carboxamide groups. With X group variation from methyl to phenyl to 4-nitrophenyl to trifluoromethyl, the acidity of the PIG is 'tuned'. Solventmore » extraction of Ag{sup +} from aqueous solutions into chloroform is used to probe the influence of structural variation within the mono-ionizable calixcrown ligand on metal ion extraction efficiency, including the identity and acidity of the PIG and its orientation with respect to the polyether ring.« less

Detection and Separation of Inorganic Cations in Natural, Potable, and Wastewater Samples Using Capillary Zone Electrophoresis with Indirect UV Detection

PubMed Central

Varden, Lara; Bou-Abdallah, Fadi

2017-01-01

Capillary zone electrophoresis (CZE) is a sensitive and rapid technique for determining traces of inorganic cations in water samples. CZE with indirect UV-diode array detection (CZE-DAD) was utilized to identify several inorganic cations in natural, potable, and wastewater samples. A pH 4.35 background electrolyte system was employed and consisted of 15 mM imidazole, 8 mM malonic acid, 2 mM 18-crown-6 ether as complexing agents, 10% v/v methanol as an organic modifier with indirect absorbance reference at 214 nm. The CZE method involved electromigration injection at 5 kV for 5 s, a separation voltage of 20 kV at 25°C, and a detection wavelength of 280 nm. Six main cations (ammonium NH4+, potassium K+, calcium Ca2+, sodium Na+, magnesium Mg2+, and lead Pb2+) were tested, and all but lead, were detected in the water samples at concentrations between 0.03 and 755 ppm with a detection limit ranging between 0.023 and 0.084 ppm. The successful evaluation of the proposed methodology allowed us to reliably detect and separate six metal ions in different water samples without any pretreatment. All water samples were collected from Northern New York towns and the Raquette River water system, the third longest river in New York State and the largest watershed of the central and western Adirondacks. PMID:29057144

Contrasting cDNA-AFLP profiles between crown and leaf tissues of cold-acclimated wheat plants indicate differing regulatory circuitries for low temperature tolerance.

PubMed

Ganeshan, Seedhabadee; Sharma, Pallavi; Young, Lester; Kumar, Ashwani; Fowler, D Brian; Chibbar, Ravindra N

2011-03-01

Low-temperature (LT) tolerance in winter wheat (Triticum aestivum L.) is an economically important but complex trait. Four selected wheat genotypes, a winter hardy cultivar, Norstar, a tender spring cultivar, Manitou and two near-isogenic lines with Vrn-A1 (spring Norstar) and vrn-A1 (winter Manitou) alleles of Manitou and Norstar were cold-acclimated at 6°C and crown and leaf tissues were collected at 0, 2, 14, 21, 35, 42, 56 and 70 days of cold acclimation. cDNA-AFLP profiling was used to determine temporal expression profiles of transcripts during cold-acclimation in crown and leaf tissues, separately to determine if LT regulatory circuitries in crown and leaf tissues could be delineated using this approach. Screening 64 primer combinations identified 4,074 and 2,757 differentially expressed transcript-derived fragments (TDFs) out of which 38 and 16% were up-regulated as compared to 3 and 6% that were down-regulated in crown and leaf tissues, respectively. DNA sequencing of TDFs revealed sequences common to both tissues including genes coding for DEAD-box RNA helicase, choline-phosphate cytidylyltransferase and delta-1-pyrroline carboxylate synthetase. TDF specific to crown tissues included genes coding for phospahtidylinositol kinase, auxin response factor protein and brassinosteroid insensitive 1-associated receptor kinase. In leaf, genes such as methylene tetrahydrofolate reductase, NADH-cytochrome b5 reductase and malate dehydrogenase were identified. However, 30 and 14% of the DNA sequences from the crown and leaf tissues, respectively, were hypothetical or unknown proteins. Cluster analysis of up-, down-regulated and unique TDFs, DNA sequence and real-time PCR validation, infer that mechanisms operating in crown and leaf tissue in response to LT are differently regulated and warrant further studies.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

Tree or canopy height is an important attribute for carbon stock estimation, forest management and habitat quality assessment. Airborne Laser Scanning (ALS) based on Light Detection and Ranging (LiDAR) has advantages over other remote sensing techniques for describing the structure of forests. However, sloped terrain can be challenging for accurate estimation of tree locations and heights based on a Canopy Height Model (CHM) generated from ALS data; a CHM is a height-normalised Digital Surface Model (DSM) obtained by subtracting a Digital Terrain Model (DTM) from a DSM. On sloped terrain, points at the same elevation on a tree crown appear to increase in height in the downhill direction, based on the ground elevations at these points. A point will be incorrectly identified as the treetop by individual tree crown (ITC) recognition algorithms if its height is greater than that of the actual treetop in the CHM, which will be recorded as the tree height. In this study, the influence of terrain slope and crown characteristics on the detection of treetops and estimation of tree heights is assessed using ALS data in a tropical forest with complex terrain (i.e. micro-topography) and tree crown characteristics. Locations and heights of 11,442 trees based on a DSM are compared with those based on a CHM. The horizontal (DH) and vertical displacements (DV) increase with terrain slope (r = 0.47 and r = 0.54 respectively, p < 0.001). The overestimations in tree height are up to 16.6 m on slopes greater than 50° in our study area in Sumatra. The errors in locations (DH) and tree heights (DV) are modelled for trees with conical and spherical tree crowns. For a spherical tree crown, DH can be modelled as R sin θ, and DV as R (sec θ - 1). In this study, a model is developed for an idealised conical tree crown, DV = R (tan θ - tan ψ), where R is the crown radius, and θ and ψ are terrain and crown angles respectively. It is shown that errors occur only when terrain angle exceeds the crown angle, with the horizontal displacement equal to the crown radius. Errors in location are seen to be greater for spherical than conical trees on slopes where crown angles of conical trees are less than the terrain angle. The results are especially relevant for biomass and carbon stock estimations in tropical forests where there are trees with large crown radii on slopes.

Exposure to volatile organic compounds and kidney dysfunction in thin film transistor liquid crystal display (TFT-LCD) workers.

PubMed

Chang, Ta-Yuan; Huang, Kuei-Hung; Liu, Chiu-Shong; Shie, Ruei-Hao; Chao, Keh-Ping; Hsu, Wen-Hsin; Bao, Bo-Ying

2010-06-15

Many volatile organic compounds (VOCs) are emitted during the manufacturing of thin film transistor liquid crystal displays (TFT-LCDs), exposure to some of which has been reported to be associated with kidney dysfunction, but whether such an effect exists in TFT-LCD industry workers is unknown. This cross-sectional study aimed to investigate the association between exposure to VOCs and kidney dysfunction among TFT-LCD workers. The results showed that ethanol (1811.0+/-1740.4 ppb), acetone (669.0+/-561.0 ppb), isopropyl alcohol (187.0+/-205.3 ppb) and propylene glycol monomethyl ether acetate (PGMEA) (102.9+/-102.0 ppb) were the four dominant VOCs present in the workplace. The 63 array workers studied had a risk of kidney dysfunction 3.21-fold and 3.84-fold that of 61 cell workers and 18 module workers, respectively. Workers cumulatively exposed to a total level of isopropyl alcohol, PGMEA and propylene glycol monomethyl ether> or =324 ppb-year had a significantly higher risk of kidney dysfunction (adjusted OR=3.41, 95% CI=1.14-10.17) compared with those exposed to <25 ppb-year after adjustment for potential confounding factors. These findings indicated that array workers might be the group at greatest risk of kidney dysfunction within the TFT-LCD industry, and cumulative exposure to specific VOCs might be associated with kidney dysfunction. Crown Copyright 2010. Published by Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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 structure is limited in the leaf-on status (the point cloud is a mainly a description of the interpolated crown surface) - the visibility of the internal crown structure in leaf-off status allows to map also the internal tree structure up to and stopping at the secondary branch level system. When combined the leaf-on and leaf-off point clouds generate a comprehensive tree crown structure description that allows a low cost and detailed 3D crown structure mapping and potentially precise biomass mapping and/or internal structural differentiation of deciduous tree species types. Compared to TLS (Terrestrial Laser Scanning) based measurements the costs are neglectable and in the range of 1500-2500 €. This suggests the approach for low cost but fine scale in-situ applications and/or projects where TLS measurements cannot be derived and for less dense forest stands where POI flights can be performed. This study used the in-copter GPS measurements for geo referencing. Better absolute geo referencing results will be obtained with DGPS reference points. The study however clearly demonstrates the potential of OTS very low cost copter systems and the image attributed GPS measurements of the copter for the automatic calculation of complex 3D point clouds in a multi temporal tree crown mapping context.

Photosensitizers derived from 132-oxo-methyl pyropheophorbide-a: enhanced effect of indium(III) as a central metal in in vitro and in vivo photosensitizing efficacy.

PubMed

Rosenfeld, Andrew; Morgan, Janet; Goswami, Lalit N; Ohulchanskyy, Tymish; Zheng, Xiang; Prasad, Paras N; Oseroff, Allan; Pandey, Ravindra K

2006-01-01

The effects of an additional keto group on absorption wavelength and the corresponding metal complexes Zn(II), Cu(II) In(III) on singlet oxygen production and photodynamic efficacy were examined among the alkyl ether analogs of pyropheophorbide-a. For the preparation of the desired photosensitizers, the methyl 13(2)-oxo-pyropheophorbide-a obtained by reacting methyl pyropheophorbide-a with aqueous LiOH-THF was converted into a series of alkyl ether analogs. These compounds were evaluated for photophysical properties and in vitro (by means of the MTT assay and intracellular localization in RIF cells) and in vivo (in C3H mice implanted with RIF tumors) photosensitizing efficacy. Among the alkyl ether derivatives, the methyl 3-decyloxyethyl-3-devinyl-13(2)-oxo-pyropheophorbide-a was found to be most effective and the insertion of In(III) into this analog further enhanced its in vitro and in vivo photosensitizing efficacy. Fluorescence microscopy showed that, in contrast to the hexyl and dodecyl ether derivatives of HPPH (which localize in mitochondria and lysosomes, respectively), the diketo-analogs and their In(III) complexes localized in Golgi bodies. The preliminary in vitro and in vivo results suggest that, in both free-base and metalated analogs, the introduction of an additional keto group at the five-member exocyclic ring in pyropheophorbide-a diminishes its photosensitizing efficacy. This may be due to a shift in subcellular localization from mitochondria to the Golgi bodies. The further introduction of In(III) enhances photoactivity, but not by shifting the localization of the photosensitizer.

Modeling tree crown dynamics with 3D partial differential equations.

PubMed

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.

Structural phase transition of magnetic [Ni(dmit)2]- salts induced by supramolecular cation structures of (M+)([12]crown-4)2.

PubMed

Akutagawa, Tomoyuki; Motokizawa, Takeshi; Matsuura, Kazumasa; Nishihara, Sadafumi; Noro, Shin-ichiro; Nakamura, Takayoshi

2006-03-30

Sandwich-type supramolecular cation structures of (M(+))([12]crown-4)(2) complexes (M(+) = Li(+), Na(+), K(+), and Rb(+)) were introduced as countercations to the [Ni(dmit)(2)](-) anion, which bears an S = (1)/(2) spin, to form novel magnetic crystals (dmit(2-) = 2-thione-1,3-dithiole-4,5-dithiolate). The zigzag arrangement of Li(+)([12]crown-4)(2) cations in Li(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salt induced weak intermolecular interactions of [Ni(dmit)(2)](-) dimers, whose magnetic spins were isolated from each other. The molecular arrangements of cations and anions in M(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salts (M(+) = Na(+), K(+), and Rb(+)) were isostructural to each other. In the case of Na(+)([12]crown-4)(2)[Ni(dmit)(2)](-), the space group C2/m changed to C2/c with a lowering in temperature from 298 to 100 K. This structural change occurred at 222.5 K as a first-order phase transition. The space group C2/m (T = 298 K) in the salt K(+)([12]crown-4)(2)[Ni(dmit)(2)](-) also changed to C2/c (T = 100 K), which transition occurred at 270 K. Crystal structural analyses at 298 and 100 K revealed changes in both supramolecular cation conformation and [Ni(dmit)(2)](-) anion arrangements. The transition from C2/m to C2/c crystals generated a dipole moment in the Na(+)([12]crown-4)(2) and K(+)([12]crown-4)(2) structures, which were reconstructed to cancel the net dipole moment of the C2/c crystals. These cation transformations led to changes in intermolecular interactions between the [Ni(dmit)(2)](-) anions via structural rearrangements. The crystal structure of C2/c was stabilized in Rb(+)([12]crown-4)(2)[Ni(dmit)(2)](-) at 298 K. The [Ni(dmit)(2)](-) configuration in these salts with the C2/c space group was a one-dimensional uniform chain, which showed the temperature-dependent magnetic susceptibility of a one-dimensional linear Heisenberg antiferromagnetic chain.

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

PubMed Central

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

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

PubMed

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.

Poly(ether ester) Ionomers as Water-Soluble Polymers for Material Extrusion Additive Manufacturing Processes.

PubMed

Pekkanen, Allison M; Zawaski, Callie; Stevenson, André T; Dickerman, Ross; Whittington, Abby R; Williams, Christopher B; Long, Timothy E

2017-04-12

Water-soluble polymers as sacrificial supports for additive manufacturing (AM) facilitate complex features in printed objects. Few water-soluble polymers beyond poly(vinyl alcohol) enable material extrusion AM. In this work, charged poly(ether ester)s with tailored rheological and mechanical properties serve as novel materials for extrusion-based AM at low temperatures. Melt transesterification of poly(ethylene glycol) (PEG, 8k) and dimethyl 5-sulfoisophthalate afforded poly(ether ester)s of sufficient molecular weight to impart mechanical integrity. Quantitative ion exchange provided a library of poly(ether ester)s with varying counterions, including both monovalent and divalent cations. Dynamic mechanical and tensile analysis revealed an insignificant difference in mechanical properties for these polymers below the melting temperature, suggesting an insignificant change in final part properties. Rheological analysis, however, revealed the advantageous effect of divalent countercations (Ca 2+ , Mg 2+ , and Zn 2+ ) in the melt state and exhibited an increase in viscosity of two orders of magnitude. Furthermore, time-temperature superposition identified an elevation in modulus, melt viscosity, and flow activation energy, suggesting intramolecular interactions between polymer chains and a higher apparent molecular weight. In particular, extrusion of poly(PEG 8k -co-CaSIP) revealed vast opportunities for extrusion AM of well-defined parts. The unique melt rheological properties highlighted these poly(ether ester) ionomers as ideal candidates for low-temperature material extrusion additive manufacturing of water-soluble parts.

Capillary break-up, gelation and extensional rheology of hydrophobically modified cellulose ethers

NASA Astrophysics Data System (ADS)

Sharma, Vivek; Haward, Simon; Pessinet, Olivia; Soderlund, Asa; Threlfall-Holmes, Phil; McKinley, Gareth

2012-02-01

Cellulose derivatives containing associating hydrophobic groups along their hydrophilic polysaccharide backbone are used extensively in the formulations for inks, water-borne paints, food, nasal sprays, cosmetics, insecticides, fertilizers and bio-assays to control the rheology and processing behavior of multi-component dispersions. These complex dispersions are processed and used over a broad range of shear and extensional rates. The presence of hydrophobic stickers influences the linear and nonlinear rheology of cellulose ether solutions. In this talk, we systematically contrast the difference in the shear and extensional rheology of a cellulose ether: ethy-hydroxyethyl-cellulose (EHEC) and its hydrophobically-modified analog (HMEHEC) using microfluidic shear rheometry at deformation rates up to 10^6 inverse seconds, cross-slot flow extensional rheometry and capillary break-up during jetting as a rheometric technique. Additionally, we provide a constitutive model based on fractional calculus to describe the physical gelation in HMEHEC solutions.

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

PubMed

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.

Submillimeter-wave Observations of Complex Organic Molecules in Southern Massive Star Forming Regions

NASA Astrophysics Data System (ADS)

Kamegai, Kazuhisa; Sakai, Takeshi; Sakai, Nami; Hirota, Tomoya; Yamamoto, Satoshi

2013-03-01

Submillimeter-wave observations of complex organic molecules toward southern massive star forming regions were carried out with ASTE 10m telescope. Methyl formate (HCOOCH3) and dimethyl ether (CH3OCH3) were detected in some molecular cloud cores with young protostars. Differences in chemical composition among neighboring cores were also found.

Unified Microscopic-Macroscopic Monte Carlo Simulations of Complex Organic Molecule Chemistry in Cold Cores

NASA Astrophysics Data System (ADS)

Chang, Qiang; Herbst, Eric

2016-03-01

The recent discovery of methyl formate and dimethyl ether in the gas phase of cold cores with temperatures as cold as 10 K challenges our previous astrochemical models concerning the formation of complex organic molecules (COMs). The strong correlation between the abundances and distributions of methyl formate and dimethyl ether further shows that current astrochemical models may be missing important chemical processes in cold astronomical sources. We investigate a scenario in which COMs and the methoxy radical can be formed on dust grains via a so-called chain reaction mechanism, in a similar manner to CO2. A unified gas-grain microscopic-macroscopic Monte Carlo approach with both normal and interstitial sites for icy grain mantles is used to perform the chemical simulations. Reactive desorption with varying degrees of efficiency is included to enhance the nonthermal desorption of species formed on cold dust grains. In addition, varying degrees of efficiency for the surface formation of methoxy are also included. The observed abundances of a variety of organic molecules in cold cores can be reproduced in our models. The strong correlation between the abundances of methyl formate and dimethyl ether in cold cores can also be explained. Nondiffusive chemical reactions on dust grain surfaces may play a key role in the formation of some COMs.

High temperature polymers for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Einsla, Brian Russel

Novel proton exchange membranes (PEMs) were investigated that show potential for operating at higher temperatures in both direct methanol (DMFC) and H 2/air PEM fuel cells. The need for thermally stable polymers immediately suggests the possibility of heterocyclic polymers bearing appropriate ion conducting sites. Accordingly, monomers and random disulfonated poly(arylene ether) copolymers containing either naphthalimide, benzoxazole or benzimidazole moieties were synthesized via direct copolymerization. The ion exchange capacity (IEC) was varied by simply changing the ratio of disulfonated monomer to nonsulfonated monomer in the copolymerization step. Water uptake and proton conductivity of cast membranes increased with IEC. The water uptake of these heterocyclic copolymers was lower than that of comparable disulfonated poly(arylene ether) systems, which is a desirable improvement for PEMs. Membrane electrode assemblies were prepared and the initial fuel cell performance of the disulfonated polyimide and polybenzoxazole (PBO) copolymers was very promising at 80°C compared to the state-of-the-art PEM (NafionRTM); nevertheless these membranes became brittle under operating conditions. Several series of poly(arylene ether)s based on disodium-3,3'-disulfonate-4,4 '-dichlorodiphenylsulfone (S-DCDPS) and a benzimidazole-containing bisphenol were synthesized and afforded copolymers with enhanced stability. Selected properties of these membranes were compared to separately prepared miscible blends of disulfonated poly(arylene ether sulfone) copolymers and polybenzimidazole (PBI). Complexation of the sulfonic acid groups with the PBI structure reduced water swelling and proton conductivity. The enhanced proton conductivity of NafionRTM membranes has been proposed to be due to the aggregation of the highly acidic side-chain sulfonic acid sites to form ion channels. A series of side-chain sulfonated poly(arylene ether sulfone) copolymers based on methoxyhydroquinone was synthesized in order to investigate this possible advantage and to couple this with the excellent hydrolytic stability of poly(arylene ether)s. The methoxy groups were deprotected to afford reactive phenolic sites and nucleophilic substitution reactions with functional aryl sulfonates were used to prepare simple aryl or highly acidic fluorinated sulfonated copolymers. The proton conductivity and water sorption of the resulting copolymers increased with the ion exchange capacity, but changing the acidity of the sulfonic acid had no apparent effect.

Coordination chemistry in magnesium battery electrolytes: how ligands affect their performance.

PubMed

Shao, Yuyan; Liu, Tianbiao; Li, Guosheng; Gu, Meng; Nie, Zimin; Engelhard, Mark; Xiao, Jie; Lv, Dongping; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun

2013-11-04

Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a study in understanding coordination chemistry of Mg(BH₄)₂ in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new electrolyte is developed based on Mg(BH₄)₂, diglyme and LiBH₄. The preliminary electrochemical test results show that the new electrolyte demonstrates a close to 100% coulombic efficiency, no dendrite formation, and stable cycling performance for Mg plating/stripping and Mg insertion/de-insertion in a model cathode material Mo₆S₈ Chevrel phase.

Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

DOE PAGES

Shao, Yuyan; Liu, Tianbiao L.; Li, Guosheng; ...

2013-11-04

Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a coordination chemistry study of Mg(BH 4) 2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new and safer electrolyte is developed based on Mg(BH4)2, diglyme and optimizedmore » LiBH4 additive. The new electrolyte demonstrates 100% coulombic efficiency, no dendrite formation, and stable cycling performance with the cathode capacity retention of ~90% for 300 cycles in a prototype magnesium battery.« less

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

DOEpatents

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

Chapter 8: Selective Stoichiometric and Catalytic Reactivity in the Confines of a Chiral Supramolecular Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth

2007-09-27

Nature uses enzymes to activate otherwise unreactive compounds in remarkable ways. For example, DNases are capable of hydrolyzing phosphate diester bonds in DNA within seconds,[1-3]--a reaction with an estimated half-life of 200 million years without an enzyme.[4] The fundamental features of enzyme catalysis have been much discussed over the last sixty years in an effort to explain the dramatic rate increases and high selectivities of enzymes. As early as 1946, Linus Pauling suggested that enzymes must preferentially recognize and stabilize the transition state over the ground state of a substrate.[5] Despite the intense study of enzymatic selectivity and ability tomore » catalyze chemical reactions, the entire nature of enzyme-based catalysis is still poorly understood. For example, Houk and co-workers recently reported a survey of binding affinities in a wide variety of enzyme-ligand, enzyme-transition-state, and synthetic host-guest complexes and found that the average binding affinities were insufficient to generate many of the rate accelerations observed in biological systems.[6] Therefore, transition-state stabilization cannot be the sole contributor to the high reactivity and selectivity of enzymes, but rather, other forces must contribute to the activation of substrate molecules. Inspired by the efficiency and selectivity of Nature, synthetic chemists have admired the ability of enzymes to activate otherwise unreactive molecules in the confines of an active site. Although much less complex than the evolved active sites of enzymes, synthetic host molecules have been developed that can carry out complex reactions with their cavities. While progress has been made toward highly efficient and selective reactivity inside of synthetic hosts, the lofty goal of duplicating enzymes specificity remains.[7-9] Pioneered by Lehn, Cram, Pedersen, and Breslow, supramolecular chemistry has evolved well beyond the crown ethers and cryptands originally studied.[10-12] Despite the increased complexity of synthetic host molecules, most assembly conditions utilize self-assembly to form complex highly-symmetric structures from relatively simple subunits. For supramolecular assemblies able to encapsulate guest molecules, the chemical environment in each assembly--defined by the size, shape, charge, and functional group availability--greatly influences the guest-binding characteristics.[6, 13-17]« less

Investigation of iron(III) complex with crown-porphyrin

NASA Astrophysics Data System (ADS)

Pankratov, Denis A.; Dolzhenko, Vladimir D.; Stukan, Reonald A.; Al Ansari, Yana F.; Savinkina, Elena V.; Kiselev, Yury M.

2013-08-01

Iron complex of 5-(4-(((4'-hydroxy-benzo-15-crown-5)-5'-yl)diazo)phenyl)-10,15,20-triphenylporphyrin was investigated by 57Fe Mössbauer 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, AFe = 0.032 cm - 1; g = 2.015, AFe = 0.0034 cm - 1. The doublet asymmetry is studied vs. temperature and normal angle to the sample plane and gamma-beam. The isomer shift δ 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, Δ ˜ 0.65 mm/s. The relax absorption may be described as a wide singlet ( δ = 0.30- 0.44 mm/s and Γ = 2.83-3.38 mm/s); its relative area strongly depends on temperature. According to δ, both signals are assigned to Fe(III).

Study on the binding characteristics of hydroxylated polybrominated diphenyl ethers and thyroid transporters using the multispectral technique and computational simulation.

PubMed

Wei, Yuchen; Yi, Zhongsheng; Xu, Jie; Yang, Wu; Yang, Lulu; Liu, Hongyan

2018-04-24

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are a class of toxic environmental pollutants that are persistent, bioaccumulative, and difficult to degrade. Their structure is very similar to the thyroid hormone (T4) and uses the body's thyroid transporter (TTR) binding to interfere with the endocrine balance, disrupting the body's normal physiological activity. According to Fourier transform infrared spectroscopy and dynamics simulation of do_dssp module analysis, there are three kinds of OH-PBDEs that can induce TTR secondary structural changes. Fluorescence spectra and UV-Vis spectra show that for the three kinds of OH-PBDEs for TTR, the main methods of quenching are static quenching and non-radiative energy transfer. According to thermodynamic analysis, ΔG < 0, ΔH > 0, and ΔS > 0 combine to show that the hydrophobic interaction is the main driving force of the combination. From the molecular docking analysis, it was found that 4'-hydroxy-2,2',4,5'- tetrabromodiphenyl ether (4'-OH-BDE49) and 4 hydroxy-2,2',3,4',5,6,6'- heptabromodiphenyl ether (4-OH-BDE188) had a cationic-π interaction with TTR, whereas 4 hydroxy-2,2',3,4,5,5',6- heptabromodiphenyl ether (4-OH-BDE187) was bonded to TTR by hydrogen bonds to form stable complexes. In this paper, we highlight the consistency of spectroscopic experiments and computer simulations so as to provide a reliable analytical method for the toxicological properties of small molecule contaminants.

40 CFR 62.1104 - Identification of sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., Contra Costa County Pulp Mill. (b) Louisiana Pacific Corp., Samoa Complex. (c) Crown Simpson Pulp Company, Fairhaven. (d) Simpson Paper Company, Shasta County Pulp Mill. [47 FR 47385, Oct. 26, 1982] Landfill Gas...

40 CFR 62.1104 - Identification of sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., Contra Costa County Pulp Mill. (b) Louisiana Pacific Corp., Samoa Complex. (c) Crown Simpson Pulp Company, Fairhaven. (d) Simpson Paper Company, Shasta County Pulp Mill. [47 FR 47385, Oct. 26, 1982] Landfill Gas...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koepf, Matthieu; Bergkamp, Jesse J.; Teillout, Anne-Lucie

The association of different metals in stable, well-defined molecular assemblies remains a great challenge of supramolecular chemistry. In such constructs, the emergence of synergism, or cooperative effects between the different metal centers is particularly intriguing. These effects can lead to uncommon reactivity or remarkable physico-chemical properties that are not otherwise achievable. For example, the association of alkaline or alkaline-earth cations and transition metals is pivotal for the activity of several biomolecules and human-made catalysts that carry out fundamental redox transformations (water oxidation, nitrogen reduction, water–gas shift reaction, etc.). In many cases the precise nature of the interactions between the alkaline-earthmore » cations and the redox-active transition metals remains elusive due to the difficulty of building stable molecular heterometallic assemblies that associate transition metals and alkaline or alkaline-earth cations in a controlled way. In this work we present the rational design of porphyrin-based ligands possessing a second binding site for alkaline-earth cations above the porphyrin macrocycle primary complexation site. We demonstrate that by using a combination of crown ether and carboxylic acid substituents suitably positioned on the periphery of the porphyrin, bitopic ligands can be obtained. The binding of calcium, a typical alkaline-earth cation, by the newly prepared ligands has been studied in detail and we show that a moderately large binding constant can be achieved in protic media using ligands that possess some degree of structural flexibility. The formation of Zn–Ca assemblies discussed in this work is viewed as a stepping stone towards the assembly of well defined molecular transition metal-alkaline earth bimetallic centers using a versatile organic scaffold.« less

Accurate Drift Time Determination by Traveling Wave Ion Mobility Spectrometry: The Concept of the Diffusion Calibration.

PubMed

Kune, Christopher; Far, Johann; De Pauw, Edwin

2016-12-06

Ion mobility spectrometry (IMS) is a gas phase separation technique, which relies on differences in collision cross section (CCS) of ions. Ionic clouds of unresolved conformers overlap if the CCS difference is below the instrumental resolution expressed as CCS/ΔCCS. The experimental arrival time distribution (ATD) peak is then a superimposition of the various contributions weighted by their relative intensities. This paper introduces a strategy for accurate drift time determination using traveling wave ion mobility spectrometry (TWIMS) of poorly resolved or unresolved conformers. This method implements through a calibration procedure the link between the peak full width at half-maximum (fwhm) and the drift time of model compounds for wide range of settings for wave heights and velocities. We modified a Gaussian equation, which achieves the deconvolution of ATD peaks where the fwhm is fixed according to our calibration procedure. The new fitting Gaussian equation only depends on two parameters: The apex of the peak (A) and the mean drift time value (μ). The standard deviation parameter (correlated to fwhm) becomes a function of the drift time. This correlation function between μ and fwhm is obtained using the TWIMS calibration procedure which determines the maximum instrumental ion beam diffusion under limited and controlled space charge effect using ionic compounds which are detected as single conformers in the gas phase. This deconvolution process has been used to highlight the presence of poorly resolved conformers of crown ether complexes and peptides leading to more accurate CCS determinations in better agreement with quantum chemistry predictions.

Triacylglycerol estolides, a new class of mammalian lipids, in the paracloacal gland of the brushtail possum (Trichosurus vulpecula).

PubMed

McLean, Stuart; Davies, Noel W; Nichols, David S; Mcleod, Bernie J

2015-06-01

The paracloacal glands are the most prevalent scent glands in marsupials, and previous investigation of their secretions in the brushtail possum (Trichosurus vulpecula) has identified many odorous compounds together with large amounts of neutral lipids. We have examined the lipids by LC-MS, generating ammonium adducts of acylglycerols by electrospray ionisation. Chromatograms showed a complex mixture of coeluting acylglycerols, with m/z from about 404 to 1048. Plots of single [M + NH4](+) ions showed three groups of lipids clearly separated by retention time. MS-MS enabled triacylglycerols and diacylglycerol ethers to be identified from neutral losses and formation of diacylglycerols and other product ions. The earliest-eluting lipids were found to be triacylglycerol estolides, in which a fourth fatty acid forms an ester link with a hydroxy fatty acid attached to the glycerol chain. This is the first report of triacylglycerol estolides in animals. They form a complex mixture with the triacylglycerols and diacylglycerol ethers of lipids with short- and long-chain fatty acids with varying degrees of unsaturation. This complexity suggests a functional role, possibly in social communication.

Oxime Ether Lipids as Transfection Agents: Assembly and Complexation with siRNA.

PubMed

Puri, Anu; Zampino, Serena; Viard, Mathias; Shapiro, Bruce A

2017-01-01

RNAi-based therapeutic approaches to combat cancer and other diseases are currently an area of great interest. However, practical applications of this approach rely on optimal tools to carry and deliver siRNA to the desired site. Oxime ether lipids (OELs) are a class of molecules among other various carriers being examined for siRNA delivery. OELs, relatively new candidates, belong to a class of non-glycerol based lipids and have begun to claim their place as an siRNA delivery carrier in the field of RNAi therapy. Chemical synthesis steps of OELs are considered relatively simple with the ability to modify the functionalities as desired. OEL-siRNA complexes can be assembled in the presence of serum-containing buffers (or cell culture media) and recent data from our and other groups have demonstrated that OELs are viable carriers for siRNA delivery in the cell culture systems. In this chapter, we provide the details of experimental protocols routinely used in our laboratory to examine OEL-siRNA complexes including their assembly, stability, and transfection efficiencies.

Abscisic acid analogs as chemical probes for dissection of abscisic acid responses in Arabidopsis thaliana.

PubMed

Benson, Chantel L; Kepka, Michal; Wunschel, Christian; Rajagopalan, Nandhakishore; Nelson, Ken M; Christmann, Alexander; Abrams, Suzanne R; Grill, Erwin; Loewen, Michele C

2015-05-01

Abscisic acid (ABA) is a phytohormone known to mediate numerous plant developmental processes and responses to environmental stress. In Arabidopsis thaliana, ABA acts, through a genetically redundant family of ABA receptors entitled Regulatory Component of ABA Receptor (RCAR)/Pyrabactin Resistant 1 (PYR1)/Pyrabactin Resistant-Like (PYL) receptors comprised of thirteen homologues acting in concert with a seven-member set of phosphatases. The individual contributions of A. thaliana RCARs and their binding partners with respect to specific physiological functions are as yet poorly understood. Towards developing efficacious plant growth regulators selective for specific ABA functions and tools for elucidating ABA perception, a panel of ABA analogs altered specifically on positions around the ABA ring was assembled. These analogs have been used to probe thirteen RCARs and four type 2C protein phosphatases (PP2Cs) and were also screened against representative physiological assays in the model plant Arabidopsis. The 1'-O methyl ether of (S)-ABA was identified as selective in that, at physiologically relevant levels, it regulates stomatal aperture and improves drought tolerance, but does not inhibit germination or root growth. Analogs with the 7'- and 8'-methyl groups of the ABA ring replaced with bulkier groups generally retained the activity and stereoselectivity of (S)- and (R)-ABA, while alteration of the 9'-methyl group afforded an analog that substituted for ABA in inhibiting germination but neither root growth nor stomatal closure. Further in vitro testing indicated differences in binding of analogs to individual RCARs, as well as differences in the enzyme activity resulting from specific PP2Cs bound to RCAR-analog complexes. Ultimately, these findings highlight the potential of a broader chemical genetics approach for dissection of the complex network mediating ABA-perception, signaling and functionality within a given species and modifications in the future design of ABA agonists. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

[Research on the aging of all-ceramics restoration materials].

PubMed

Zhang, Dongjiao; Chen, Xinmin

2011-10-01

All-ceramic crowns and bridges have been widely used for dental restorations owing to their excellent functionality, aesthetics and biocompatibility. However, the premature clinical failure of all-ceramic crowns and bridges may easily occur when they are subjected to the complex environment of oral cavity. In the oral environment, all-ceramic materials are prone to aging. Aging can lead all-ceramic materials to change color, to lower bending strength, and to reduce anti-fracture toughness. There are many factors affecting the aging of the all-ceramic materials, for example, the grain size, the type of stabilizer, the residual stress and the water environment. In order to analyze the aging behavior, to optimize the design of all-ceramic crowns and bridges, and to evaluate the reliability and durability, we review in this paper recent research progress of aging behavior for all-ceramics restoration materials.

(18-Crown-6)potassium [(1,2,5,6-η)-cyclo-octa-1,5-diene][(1,2,3,4-η)-naph-tha-lene]-ferrate(-I).

PubMed

Brennessel, William W; Ellis, John E

2012-10-01

The title salt, [K(C(12)H(24)O(6))][Fe(C(8)H(12))(C(10)H(8))], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(-I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclo-octa-diene, 18-crown-6 = 1,4,7,10,13,16-hexa-oxacyclo-octa-deca-ne). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetra-hedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°.

Circumferential fit assessment of CAD/CAM single crowns--a pilot investigation on a new virtual analytical protocol.

PubMed

Matta, Ragai E; Schmitt, Johannes; Wichmann, Manfred; Holst, Stefan

2012-10-01

Techniques currently applied to determine the marginal accuracy of dental crown restorations yield inadequate information. This investigation aimed to test a new virtual approach for determining the precision of fit of single-crown copings. Zirconia single crown copings were manufactured on 10 gypsum, single-tooth master casts with two different established computer-aided design/computer-assisted manufacture (CAD/CAM) systems (groups A and B). After cementation, the circumferential fit was assessed with an industrial noncontact scanner and virtual 3D analysis, following a triple-scan protocol. Marginal fit was determined by virtual sectioning; each abutment-coping complex was digitally sliced in 360 vertical sections (1 degree per section). Standardized measurement distances for analyzing the marginal fit (z, xy, xyz) were selected, and a crosshair alignment was utilized to determine whether crowns were horizontally and/or vertically too large or small. The Mann-Whitney test was applied to test for differences between groups. Significant differences in the xy direction (P = .008) were measured between groups. Group A showed a greater number of horizontally overextended margins and a higher frequency of xy distances greater than 150 Μm, in addition to a tendency for excessive z distances (P = .095). The mean marginal gap values were clinically acceptable in the present investigation; however, a full circumferential analysis revealed significant differences in marginal coping quality.

Preparation and characterization of chitosan membranes by using a combined freeze gelation and mild crosslinking method.

PubMed

Orrego, Carlos E; Valencia, Jesús S

2009-02-01

When gelification is performed by freezing-thawing repeated cycles, the resultant gel-like polymer systems are called cryogels. This work aims to assess the effect of the addition of glutaraldehyde and 18 Crown Ether-6 on surface properties and protein loading of dried chitosan cryogel films. Residual water content of treated chitosan membranes ranged between 11.93 and 13.86%, while their water activities vary from 0.5 to 0.7 (measured from 4 to 60 degrees C). Based on thermal data, water evaporation peak and degradation temperatures of chitosan membranes shifted to a higher temperature for crosslinked samples. X-ray diffractograms provide high values of crystallinity for all the samples (70.67-92.86%), the highest value being for the glutaraldehyde-treated membrane. Candida rugosa lipase can be immobilized successfully on chitosan membranes. Lipase immobilized on glutaraldehyde-crosslinked chitosan yielded the highest efficiency in terms of total coupled protein and protein loading efficiency.

Effects of chemical form of sodium on the product characteristics of alkali lignin pyrolysis.

PubMed

Guo, Da-liang; Yuan, Hong-you; Yin, Xiu-li; Wu, Chuang-zhi; Wu, Shu-bin; Zhou, Zhao-qiu

2014-01-01

The effects of Na as organic bound form or as inorganic salts form on the pyrolysis products characteristics of alkali lignin were investigated by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR), tube furnace and thermo-gravimetric analyzer (TGA). Results of TG-FTIR and tube furnace indicated that the two chemical forms Na reduced the releasing peak temperature of CO and phenols leading to the peak temperature of the maximum mass loss rate shifted to low temperature zone. Furthermore, organic bound Na obviously improved the elimination of alkyl substituent leading to the yields of phenol and guaiacol increased, while inorganic Na increased the elimination of phenolic hydroxyl groups promoting the formation of ethers. It was also found the two chemical forms Na had different effects on the gasification reactivity of chars. For inorganic Na, the char conversion decreased with increasing the char forming temperature, while organic bound Na was opposite. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Determination of volatile corrosion inhibitors by capillary electrophoresis.

PubMed

Pereira, Elisabete A; Tavares, Marina F M

2004-10-08

In this work, a capillary electrophoresis (CE) method using indirect UV detection (214nm) for the simultaneous determination of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethylethanolamine (DEEA), monocyclohexylamine (MCHA) and dicyclohexylamine (DCHA) in water/ethanol extracts of wrapping materials containing volatile corrosion inhibitors (VCIs) was described. A running buffer consisting of 0.010 molL(-1) imidazole, 0.010 molL(-1) 2-hydroxyisobutyric acid (HIBA) and 0.010 molL(-1) 18-crown-6 ether enabled separation of the analytes in less than 7 min. A few method validation parameters were determined revealing good migration time repeatability (<0.7% RSD) and area repeatability (< 1.8% RSD). Limits of detection were in the range of 0.52-1.54 mg L(-1). Recovery values were in the range of 94.8-100.9%. The methodology was successfully applied to the analysis of three commercial products (VCI treated paper, foam and plastic). The concentration of amines in these materials varied from 0.050 to 22.3% (w/w).

Effect of Additives on the Selectivity and Reactivity of Enzymes.

PubMed

Liang, Yi-Ru; Wu, Qi; Lin, Xian-Fu

2017-01-01

Enzymes have been widely used as efficient, eco-friendly, and biodegradable catalysts in organic chemistry due to their mild reaction conditions and high selectivity and efficiency. In recent years, the catalytic promiscuity of many enzymes in unnatural reactions has been revealed and studied by chemists and biochemists, which has expanded the application potential of enzymes. To enhance the selectivity and activity of enzymes in their natural or promiscuous reactions, many methods have been recommended, such as protein engineering, process engineering, and media engineering. Among them, the additive approach is very attractive because of its simplicity to use and high efficiency. In this paper, we will review the recent developments about the applications of additives to improve the catalytic performances of enzymes in their natural and promiscuous reactions. These additives include water, organic bases, water mimics, cosolvents, crown ethers, salts, surfactants, and some particular molecular additives. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Determination of inorganic ions in explosive residues by capillary zone electrophoresis].

PubMed

Feng, Junhe; Guo, Baoyuan; Lin, Jin-Ming; Xu, Jianzhong; Zhou, Hong; Sun, Yuyou; Liu, Yao; Quan, Yangke; Lu, Xiaoming

2008-11-01

Five anions (chlorate, perchlorate, nitrate, nitrite, and sulfate) and two cations (ammonium and potassium) in explosive residues have been separated and determined by capillary zone electrophoresis (CZE) with indirect ultraviolet detection. The electrolyte buffer for the cation separation was 10 mmol/L pyridine (pH 4.5) -3 mmol/L 18-crown-6-ether. Ammonium and potassium ions were baseline separated in less than 2.6 min with the detection limits of 0.10 mg/L and 0.25 mg/L (S/N = 3), respectively. The electrolyte buffer for the anion separation consisted of 40 mmol/L boric acid-1.8 mmol/L potassium dichromate-2 mmol/L sodium tetraborate (pH 8.6), and tetramethyl ammonium hydroxide (TMAOH) was used as electroosmotic flow modifier. All five anions were well separated in less than 4.6 min with the detection limit range of 0.10 - 1.85 mg/L (S/N = 3). The method was successfully used in real sample investigations to confirm the type of explosives.

Reversible mechanical protection: building a 3D “suit” around a T-shaped benzimidazole axle† †Electronic supplementary information (ESI) available: Synthetic details and full characterisation of all new compounds. CCDC 1533271 and 1533272. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00790f Click here for additional data file. Click here for additional data file.

PubMed Central

Baggi, Giorgio; Vukotic, V. Nicholas

2017-01-01

The T-shaped benzimidazolium/crown ether recognition motif was used to prepare suit[1]anes. These novel mechanically interlocked molecules (MIMs) were fully characterized by 1H and 13C NMR spectroscopy, single-crystal X-ray diffraction, UV-vis absorption and fluorescence spectroscopy. By conversion to a suit[1]ane, a simple benzimidazole was shown to be protected from deprotonation by strong base. Moreover, it was demonstrated that this unique three-dimensional encapsulation can be made reversible, thus introducing the concept of “reversible mechanical protection”; a protecting methodology that may have potential applications in synthetic organic chemistry and the design of molecular machinery. PMID:28626559

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery.

PubMed

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-02-06

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

PubMed Central

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-01-01

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

Ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 2. Photoinduced electron transfer to counterions in solution.

PubMed

Bragg, Arthur E; Schwartz, Benjamin J

2008-04-24

The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by other factors that alter the solution environment local to the CTTS anion, including the presence of cosolutes, cosolvents, and other ions. In this paper, we examine the ultrafast CTTS dynamics of iodide in liquid tetrahydrofuran (THF) with a particular focus on how the solvent dynamics and the CTTS electron-ejection process are altered in the presence of various counterions. In weakly polar solvents such as THF, iodide salts can be strongly ion-paired in solution; the steady-state UV-visible absorption spectroscopy of various iodide salts in liquid THF indicates that the degree of ion-pairing changes from strong to weak to none as the counterion is switched from Na+ to tetrabutylammonium (t-BA+) to crown-ether-complexed Na+, respectively. In our ultrafast experiments, we have excited the I- CTTS transition of these various iodide salts at 263 nm and probed the dynamics of the CTTS-detached electrons throughout the visible and near-IR. In the previous paper of this series (Bragg, A. E.; Schwartz, B. J. J. Phys. Chem. B 2008, 112, 483-494), we found that for "counterion-free" I- (obtained by complexing Na+ with a crown ether) the CTTS electrons were ejected approximately 6 nm from their partner iodine atoms, the result of significant nonadiabatic coupling between the CTTS excited state and extended electronic states supported by the naturally existing solvent cavities in liquid THF, which also serve as pre-existing electron traps. In contrast, for the highly ion-paired NaI/THF system, we find that approximately 90% of the CTTS electrons are "captured" by a nearby Na+ to form (Na+, e-)THF "tight-contact pairs" (TCPs), which are chemically and spectroscopically distinct from both solvated neutral sodium atoms and free solvated electrons. A simple kinetic model is able to reproduce the details of the electron capture process, with 63% of the electrons captured quickly in approximately 2.3 ps, 26% captured diffusively in approximately 63 ps, and the remaining 11% escaping out into the solution on subnanosecond time scales. We also find that the majority of the CTTS electrons are ejected to within 1 or 2 nm of the Na+. This demonstrates that the presence of the nearby cation biases the relocalization of CTTS-generated electrons from I- in THF, changing the nonadiabatic coupling to the extended, cavity-supported electronic states in THF to produce a much tighter distribution of electron-ejection distances. In the case of the more loosely ion-paired t-BA+-I-/THF system, we find that only 10-15% of the CTTS-ejected electrons associate with t-BA+ to form "loose-contact pairs" (LCPs), which are characterized by a much weaker interaction between the electron and cation than occurs in TCPs. The formation of (t-BA+, e-)THF LCPs is characterized by a Coulombically induced blue shift of the free eTHF- spectrum on a approximately 5-ps time scale. We argue that the weaker interaction between t-BA+ and the parent I- results in little change to the CTTS-ejection process, so that only those electrons that happen to localize in the vicinity of t-BA+ are captured to form LCPs. Finally, we interpret the correlation between electron capture yield and counterion-induced perturbation of the I- CTTS transition as arising from changes in the distribution of ion-pair separations with cation identity, and we discuss our results in the context of relevant solution conductivity measurements.

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

PubMed

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.

Identification of number and type of cations in water-soluble Cs+ and Na+ calix[4]arene-bis-crown-6 complexes by using ESI-TOF-MS.

PubMed

Kumagai, Shogo; Hayashi, Kotaro; Kameda, Tomohito; Morohashi, Naoya; Hattori, Tetsutaro; Yoshioka, Toshiaki

2018-04-01

The treatment of cesium-contaminated wastewater has become one of the biggest issues. The selective Cs + removal from wastewater containing competitive alkali metal ions such as Na + is desired to reduce the volume of sludge. Therefore, the present work focused on water-soluble calix[4]arene-bis-crown-6 (W-BisC6) to selectively capture Cs + . For characterization of the complex, UV-vis spectroscopy is commonly used, however, due to the limited availability of information it can be hard to quickly identify the specific structures of some complexes. In this work, the electrospray ionization time of flight spectrometry (ESI-TOF-MS) is successfully utilized to identify the number and type of cations in W-BisC6-cation complexes. ESI-TOF-MS accurately recognized 4 types of complex (W-BisC6-Na + , W-BisC6-Cs + , W-BisC6-2Na + , W-BisC6-Na + -Cs + ), and the experimental and simulated results were almost perfectly matched. It also revealed the difficulty of W-BisC6-2Cs + complex formation under the present conditions. Thus, this technique is significantly helpful for rapid identification of the specific structures of complexes during Cs + -contaminated wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

40 CFR Table 6 to Subpart Jj of... - VHAP of Potential Concern

Code of Federal Regulations, 2011 CFR

2011-07-01

... glycol butyl ether, ethylene glycol ethyl ether (2-ethoxy ethanol), ethylene glycol hexyl ether, ethylene..., ethylene glycol mono-2-ethylhexyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether... glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol...

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

NASA Astrophysics Data System (ADS)

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

2007-05-01

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 and predict the strip crown, a new customized semi-analytical modeling technique that couples the Finite Element Method (FEM) with classical solid mechanics was developed to model the deflection of the rolls and strip while under load. The technique employed offers several important advantages over traditional methods to calculate strip crown, including continuity of elastic foundations, non-iterative solution when using predetermined foundation moduli, continuous third-order displacement fields, simple stress-field determination, and a comparatively faster solution time.

Synthesis and Characterization of Potassium Aryl- and Alkyl-Substituted Silylchalcogenolate Salts

DOE PAGES

Brown, Jessica Lynn; Montgomery, Ashley C.; Samaan, Christopher A.; ...

2016-02-23

Treatment of either triphenyl(chloro)silane or tert-butyldiphenyl(chloro)silane with potassium metal in THF, followed by addition of 18-crown-6, affords [K(18-crown-6)][SiPh 3] (1) and [K(18-crown-6)][SiPh 2 tBu] (2), respectively, as the reaction products in high yield. Compounds 1 and 2 were fully characterized including by multi-nuclear NMR and IR spectroscopies. Addition of elemental chalcogen to either 1 or 2, results in facile chalcogen insertion into the potassium-silicon bond to afford the silylchalcogenolates, [K(18-crown-6)][E– SiPh2R] (E = S, R = Ph (3); Se, R = Ph (4); E = Te, R = Ph (5); E = S, R = tBu (6); E = Se,more » R = tBu (7); E = Te, R = tBu (8)), in moderate to good yield. The silylchalcogenolates reported herein were characterized by multi-nuclear NMR and IR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the reported compounds crystallize as discrete monomers in the solid-state, a structural feature not previously observed in silylchalcogenolates, providing well-defined access routes into systematic metal complexation studies.« less

Isolation of homoleptic platinum oxyanionic complexes with doubly protonated diazacrown cation

NASA Astrophysics Data System (ADS)

Vasilchenko, Danila; Tkachev, Sergey; Baidina, Iraida; Romanenko, Galina; Korenev, Sergey

2017-02-01

Doubly protonated diazacrown ether cation (1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane DCH22+) was used for the efficient isolation of the homoleptic platinum complexes [Pt(NO3)6]2- and [Pt(C2O4)2]2- to crystalline solid phases from solutions containing mixtures of related platinum complexes. DCH22+ molecules in nitric acid solution were shown to prevent the condensation of mononuclear [Pt(H2O)n(NO3)6-n]n-2 species.

Encapsulation of atmospheric CO2 by a self-assembled decanuclear cadmium complex via unfamiliar perchlorato and carbonato bridges.

PubMed

García-Deibe, Ana M; Portela-García, Cristina; Fondo, Matilde; Mota, Antonio J; Sanmartín-Matalobos, Jesús

2012-10-11

A decanuclear Cd complex has been found as a carbonate-containing capsule. The structure strongly resembles a ten-blade waterwheel with a central carbonate ligand surrounded by two superimposed Cd(5)O(5) crowns with a pentagonal antiprism-like disposition. The capsule is doubly capped by two pentadentate perchlorate anions.

Tubular Unimolecular Transmembrane Channels: Construction Strategy and Transport Activities.

PubMed

Si, Wen; Xin, Pengyang; Li, Zhan-Ting; Hou, Jun-Li

2015-06-16

Lipid bilayer membranes separate living cells from their environment. Membrane proteins are responsible for the processing of ion and molecular inputs and exports, sensing stimuli and signals across the bilayers, which may operate in a channel or carrier mechanism. Inspired by these wide-ranging functions of membrane proteins, chemists have made great efforts in constructing synthetic mimics in order to understand the transport mechanisms, create materials for separation, and develop therapeutic agents. Since the report of an alkylated cyclodextrin for transporting Cu(2+) and Co(2+) by Tabushi and co-workers in 1982, chemists have constructed a variety of artificial transmembrane channels by making use of either the multimolecular self-assembly or unimolecular strategy. In the context of the design of unimolecular channels, important advances have been made, including, among others, the tethering of natural gramicidin A or alamethicin and the modification of various macrocycles such as crown ethers, cyclodextrins, calixarenes, and cucurbiturils. Many of these unimolecular channels exhibit high transport ability for metal ions, particularly K(+) and Na(+). Concerning the development of artificial channels based on macrocyclic frameworks, one straightforward and efficient approach is to introduce discrete chains to reinforce their capability to insert into bilayers. Currently, this approach has found the widest applications in the systems of crown ethers and calixarenes. We envisioned that for macrocycle-based unimolecular channels, control of the arrangement of the appended chains in the upward and/or downward direction would favor the insertion of the molecular systems into bilayers, while the introduction of additional interactions among the chains would further stabilize a tubular conformation. Both factors should be helpful for the formation of new efficient channels. In this Account, we discuss our efforts in designing new unimolecular artificial channels from tubular pillar[n]arenes by extending their lengths with various ester, hydrazide, and short peptide chains. We have utilized well-defined pillar[5]arene and pillar[6]arene as rigid frameworks that allow the appended chains to afford extended tubular structures. We demonstrate that the hydrazide and peptide chains form intramolecular N-H···O═C hydrogen bonds that enhance the tubular conformation of the whole molecule. The new pillar[n]arene derivatives have been successfully applied as unimolecular channels for the selective transport of protons, water, and amino acids and the voltage-gated transport of K(+). We also show that aromatic hydrazide helices and macrocycles appended with peptide chains are able to mediate the selective transport of NH4(+).

Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

DOEpatents

Hofmann, Michael A.

2006-11-14

The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

Reductive Etherification of Fatty Acids or Esters with Alcohols using Molecular Hydrogen.

PubMed

Erb, Benjamin; Risto, Eugen; Wendling, Timo; Gooßen, Lukas J

2016-06-22

In the presence of a catalyst system consisting of a ruthenium/triphos complex and the Brønsted acid trifluoromethanesulfonimide, mixtures of fatty acids and aliphatic alcohols are converted into the corresponding ethers at 70 bar H2 . The protocol allows the sustainable one-step synthesis of valuable long-chain ether fragrances, lubricants, and surfactants from renewable sources. The reaction protocol is extended to various fatty acids and esters both in pure form and as mixtures, for example, tall oil acids or rapeseed methyl ester (RME). Even the mixed triglyceride rapeseed oil was converted in one step. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a poly (ether urethane) system for the controlled release of two novel anti-biofilm agents based on gallium or zinc and its efficacy to prevent bacterial biofilm formation

PubMed Central

Ma, Hongyan; Darmawan, Erica T.; Zhang, Min; Zhange, Lei; Bryers, James D.

2013-01-01

Traditional antibiotic therapy to control medical device-based infections typically fails to clear biofilm infections and may even promote the evolution of antibiotic resistant species. We report here the development of two novel antibiofilm agents; gallium (Ga) or zinc (Zn) complexed with protoporphyrin IX (PP) or mesoprotoporphyrin IX (MP) that are both highly effective in negating suspended bacterial growth and biofilm formation. These chelated gallium or zinc complexes act as iron siderophore analogs, surplanting the natural iron uptake of most bacteria. Poly (ether urethane) (PEU; Biospan®) polymer films were fabricated for the controlled sustained release of the Ga- or Zn-complexes, using an incorporated pore-forming agent, poly (ethylene glycol) (PEG). An optimum formulation containing 8% PEG (MW=1450) in the PEU polymer effectively sustained drug release for at least 3 months. All drug-loaded PEU films exhibited in vitro ≥ 90% reduction of Gram-positive (Staphylococcus epidermidis) and Gram-negative (Pseudomonas aeruginosa) bacteria in both suspended and biofilm culture versus the negative control PEU films releasing nothing. Cytotoxicity and endotoxin evaluation demonstrated no adverse responses to the Ga- or Zn-complex releasing PEU films. Finally, in vivo studies further substantiate the anti-biofilm efficacy of the PEU films releasing Ga- or Zn- complexes. PMID:24140747

Development of a poly(ether urethane) system for the controlled release of two novel anti-biofilm agents based on gallium or zinc and its efficacy to prevent bacterial biofilm formation.

PubMed

Ma, Hongyan; Darmawan, Erica T; Zhang, Min; Zhang, Lei; Bryers, James D

2013-12-28

Traditional antibiotic therapy to control medical device-based infections typically fails to clear biofilm infections and may even promote the evolution of antibiotic resistant species. We report here the development of two novel antibiofilm agents; gallium (Ga) or zinc (Zn) complexed with protoporphyrin IX (PP) or mesoprotoporphyrin IX (MP) that are both highly effective in negating suspended bacterial growth and biofilm formation. These chelated gallium or zinc complexes act as iron siderophore analogs, supplanting the natural iron uptake of most bacteria. Poly (ether urethane) (PEU; Biospan®) polymer films were fabricated for the controlled sustained release of the Ga- or Zn-complexes, using an incorporated pore-forming agent, poly(ethylene glycol) (PEG). An optimum formulation containing 8% PEG (MW=1450) in the PEU polymer effectively sustained drug release for at least 3months. All drug-loaded PEU films exhibited in vitro ≥ 90% reduction of Gram-positive (Staphylococcus epidermidis) and Gram-negative (Pseudomonas aeruginosa) bacteria in both suspended and biofilm culture versus the negative control PEU films releasing nothing. Cytotoxicity and endotoxin evaluation demonstrated no adverse responses to the Ga- or Zn-complex releasing PEU films. Finally, in vivo studies further substantiate the anti-biofilm efficacy of the PEU films releasing Ga- or Zn- complexes. © 2013.

On the Formation of the C2H6O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I.

2017-06-01

The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

Solvent extraction of Li+, H3O+ and NH4+ into nitrobenzene by using sodium dicarbollylcobaltate and calix[4]arene-bis(t-octylbenzo-18-crown-6)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makrlik, Emanuel; Selucky, P.; Vanura, Petr

2013-01-01

From extraction experiments and c-activity measurements, the exchange extraction constants corresponding to the general equilibrium M+ (aq) + NaL+ (nb) , ML+ (nb) + Na+ (aq) taking place in the two-phase water nitrobenzene system (M+ = Li+, H3O+, NH+4; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML+ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: zH3O+ < Li+ < NH+4.

Mesenchymal Stem Cell-Mediated Functional Tooth Regeneration in Swine

PubMed Central

Fang, Dianji; Yamaza, Takayoshi; Seo, Byoung-Moo; Zhang, Chunmei; Liu, He; Gronthos, Stan; Wang, Cun-Yu; Shi, Songtao; Wang, Songlin

2006-01-01

Mesenchymal stem cell-mediated tissue regeneration is a promising approach for regenerative medicine for a wide range of applications. Here we report a new population of stem cells isolated from the root apical papilla of human teeth (SCAP, stem cells from apical papilla). Using a minipig model, we transplanted both human SCAP and periodontal ligament stem cells (PDLSCs) to generate a root/periodontal complex capable of supporting a porcelain crown, resulting in normal tooth function. This work integrates a stem cell-mediated tissue regeneration strategy, engineered materials for structure, and current dental crown technologies. This hybridized tissue engineering approach led to recovery of tooth strength and appearance. PMID:17183711

Modeling of multiple equilibria in the self-aggregation of di-n-decyldimethylammonium chloride/octaethylene glycol monododecyl ether/cyclodextrin ternary systems.

PubMed

Leclercq, Loïc; Lubart, Quentin; Aubry, Jean-Marie; Nardello-Rataj, Véronique

2013-05-28

The surface tension equations of binary surfactant mixtures (di-n-decyldimethylammonium chloride and octaethylene glycol monododecyl ether) are established by combining the Szyszkowski equation of surfactant solutions, the ideal or nonideal mixing theory, and the phase separation model. For surfactant mixtures, the surface tension at the air-water interface is calculated using nonideal theory due to synergism between the two adsorbed surfactant types. The incorporation of cyclodextrin complexation model to the surface tension equations gives a robust model for the description of the surface tension isotherms of binary, ternary, and more complex systems involving numerous inclusion complexes. The surface tension data obtained experimentally shows excellent agreement with the theoretical model below and above the formation of micelles. The strong synergistic effect observed between the two surfactants is disrupted by the presence of CDs, leading to ideal behavior of ternary systems. Indeed, depending on the nature of the cyclodextrin (i.e., α, β, or γ), which allows a tuning of the cavity size, the binding constants with the surfactants are modified as well as the surface properties due to strong modification of equilibria involved in the ternary mixture.

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

NASA Astrophysics Data System (ADS)

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.

Novel melt-processable poly(ether ether ketone)(PEEK)/inorganic fullerene-like WS(2) nanoparticles for critical applications.

PubMed

Naffakh, Mohammed; Díez-Pascual, Ana M; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2010-09-09

The combination of high-performance thermoplastic poly(ether ether ketone) (PEEK) with inorganic fullerene-like tungsten disulfide (IF-WS(2)) nanoparticles offers an attractive way to combine the merits of organic and inorganic materials into novel polymer nanocomposite materials. Here, we report the processing of novel PEEK/IF-WS(2) nanocomposites, which overcome the nanoparticle agglomerate formation and provide PEEK-particle interactions. The IF-WS(2) nanoparticles do not require exfoliation or modification, making it possible to obtain stronger, lighter materials without the complexity and processing cost associated with these treatments. The nanocomposites were fabricated by melt blending, after a predispersion step based on ball milling and mechanical treatments in organic solvent, which leads to the dispersion of individually IF-WS(2) nanoparticles in the PEEK matrix as confirmed by scanning electron microscopy. In order to determine the performance of the PEEK/IF-WS(2) nanocomposites for potential critical applications, particularly for the aircraft industry, we have extensively investigated these materials with a wide range of structural, thermal, and mechanical techniques using time-resolved synchrotron X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, dynamic-mechanical analysis, and tensile and impact tests as well as thermal measurements. Modulus, tensile strengh, thermal stability, and thermal conductivity of PEEK exhibited remarkable improvement with the addition of IF-WS(2).

The historical significance of anaesthesia events at Pearl Harbor.

PubMed

Crowhurst, Ja

2014-07-01

Up to the end of World War II, less than 10% of the general anaesthetics administered was with intravenous barbiturates. The remaining 90% of anaesthetics given in the USA were with diethyl ether. In the United Kingdom and elsewhere, chloroform was also popular. Diethyl ether administration was a relatively safe and simple procedure, often delegated to nurses or junior doctors with little or no specific training in anaesthesia. During the Japanese attack on the US bases at Pearl Harbor, with reduced stocks of diethyl ether available, intravenous Sodium Pentothal(®), a most 'sophisticated and complex' drug, was used with devastating effects in many of those hypovolaemic, anaemic and septic patients. The hazards of spinal anaesthesia too were realised very quickly. These effects were compounded by the dearth of trained anaesthetists. This paper presents the significance of the anaesthesia tragedies at Pearl Harbor, and the discovery in the next few years of many other superior drugs that caused medical and other health professionals to realise that anaesthesia needed to be a specialist medical discipline in its own right. Specialist recognition, aided by the foundation of the National Health Service in the UK, the establishment of Faculties of Anaesthesia and appropriate training in pharmacology, physiology and other sciences soon followed. Modern anaesthesiology, as we understand it today, was born and a century or more of ether anaesthesia finally ceased.

Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings

NASA Astrophysics Data System (ADS)

Topa, Monika; Ortyl, Joanna; Chachaj-Brekiesz, Anna; Kamińska-Borek, Iwona; Pilch, Maciej; Popielarz, Roman

2018-06-01

Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.

Aesthetic Rehabilitation of a Complicated Crown-Root Fracture of the Maxillary Incisor: Combination of Orthodontic and Implant Treatment

PubMed Central

de Avila, Érica Dorigatti; de Molon, Rafael Scaf; Cardoso, Mauricio de Almeida; Capelozza Filho, Leopoldino; Campos Velo, Marilia Mattar de Amoêdo; Mollo, Francisco de Assis; Borelli Barros, Luiz Antonio

2014-01-01

The aim of this paper is to present a complex rehabilitation, of fractured tooth, with implants in anterior region considering the orthodontics extrusion to clinical success. At 7 years old, the patient fractured the maxillary left central incisor and the dentist did a crown with the fragment. Twenty years later, the patient was referred to a dental clinic for orthodontic treatment, with the chief complaint related to an accentuated deep bite, and a professional started an orthodontic treatment. After sixteen months of orthodontic treatment, tooth 21 fractured. The treatment plan included an orthodontic extrusion of tooth 21 and implant placement. This case has been followed up and the clinical and radiographic examinations show excellence esthetic results and satisfaction of patient. The forced extrusion can be a viable treatment option in the management of crown root fracture of an anterior tooth to gain bone in a vertical direction. This case emphasizes that to achieve the esthetic result a multidisciplinary approach is necessary. PMID:24872900

(18-Crown-6)potassium [(1,2,5,6-η)-cyclo­octa-1,5-diene][(1,2,3,4-η)-naph­tha­lene]­ferrate(−I)

PubMed Central

Brennessel, William W.; Ellis, John E.

2012-01-01

The title salt, [K(C12H24O6)][Fe(C8H12)(C10H8)], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(−I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclo­octa­diene, 18-crown-6 = 1,4,7,10,13,16-hexa­oxacyclo­octa­deca­ne). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetra­hedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°. PMID:23125569

Synthesis and Characterization of Hydrophilic-Hydrophobic Poly(Arylene Ether Sulfone) Random and Segmented Copolymers for Membrane Applications

NASA Astrophysics Data System (ADS)

Nebipasagil, Ali

Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamideterminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDELRTM foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and a,u-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivity of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and alpha,o-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology.

UrbanCrowns: an assessment and monitoring tool for urban trees

Treesearch

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

2011-01-01

UrbanCrowns is a Windows®-based computer program used to assess the crown characteristics of urban trees. The software analyzes side-view digital photographs of trees to compute several crown metrics, including crown height, crown diameter, live crown ratio, crown volume, crown density, and crown transparency. Potential uses of the UrbanCrowns program include...

Development of the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) Process for Cesium Removal from High-Level Tank Waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Bruce A; Bonnesen, Peter V; Delmau, Laetitia Helene

2011-01-01

This paper describes the chemical performance of the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process in its current state of development for removal of cesium from the alkaline high-level tank wastes at the Savannah River Site (SRS) in the US Department of Energy (USDOE) complex. Overall, motivation for seeking a major enhancement in performance for the currently deployed CSSX process stems from needs for accelerating the cleanup schedule and reducing the cost of salt-waste disposition. The primary target of the NG-CSSX development campaign in the past year has been to formulate a solvent system and to design a corresponding flowsheet thatmore » boosts the performance of the SRS Modular CSSX Unit (MCU) from a current minimum decontamination factor of 12 to 40,000. The chemical approach entails use of a more soluble calixarene-crown ether, called MaxCalix, allowing the attainment of much higher cesium distribution ratios (DCs) on extraction. Concurrently decreasing the Cs-7SB modifier concentration is anticipated to promote better hydraulics. A new stripping chemistry has been devised using a vitrification-friendly aqueous boric acid strip solution and a guanidine suppressor in the solvent, resulting in sharply decreased DCs on stripping. Results are reported herein on solvent phase behavior and batch Cs distribution for waste simulants and real waste together with a preliminary flowsheet applicable for implementation in the MCU. The new solvent will enable MCU to process a much wider range of salt feeds and thereby extend its service lifetime beyond its design life of three years. Other potential benefits of NG-CSSX include increased throughput of the SRS Salt Waste Processing Facility (SWPF), currently under construction, and an alternative modular near-tank application at Hanford.« less

Identification of inorganic ions in post-blast explosive residues using portable CE instrumentation and capacitively coupled contactless conductivity detection.

PubMed

Hutchinson, Joseph P; Johns, Cameron; Breadmore, Michael C; Hilder, Emily F; Guijt, Rosanne M; Lennard, Chris; Dicinoski, Greg; Haddad, Paul R

2008-11-01

Novel CE methods have been developed on portable instrumentation adapted to accommodate a capacitively coupled contactless conductivity detector for the separation and sensitive detection of inorganic anions and cations in post-blast explosive residues from homemade inorganic explosive devices. The methods presented combine sensitivity and speed of analysis for the wide range of inorganic ions used in this study. Separate methods were employed for the separation of anions and cations. The anion separation method utilised a low conductivity 70 mM Tris/70 mM CHES aqueous electrolyte (pH 8.6) with a 90 cm capillary coated with hexadimethrine bromide to reverse the EOF. Fifteen anions could be baseline separated in 7 min with detection limits in the range 27-240 microg/L. A selection of ten anions deemed most important in this application could be separated in 45 s on a shorter capillary (30.6 cm) using the same electrolyte. The cation separation method was performed on a 73 cm length of fused-silica capillary using an electrolyte system composed of 10 mM histidine and 50 mM acetic acid, at pH 4.2. The addition of the complexants, 1 mM hydroxyisobutyric acid and 0.7 mM 18-crown-6 ether, enhanced selectivity and allowed the separation of eleven inorganic cations in under 7 min with detection limits in the range 31-240 microg/L. The developed methods were successfully field tested on post-blast residues obtained from the controlled detonation of homemade explosive devices. Results were verified using ion chromatographic analyses of the same samples.

Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment† †Electronic supplementary information (ESI) available: Additional computational details, spectroscopic information, crystallographic data collection, structure solution, and refinement (PDF), X-ray diffraction details of compounds 1-Ln (Ln = Nd, Gd, Dy, and Er), 2-Nd, 2-Ln/3-Ln (Ln = Gd, Dy, Er), 2-Dy/4-Dy, and 5-Dy/6-Dy. CCDC (CIF, 1538987–1538995 and 1566075 for 2-Dy/3-Dy), and DFT-optimized structural coordinates for 2-Nd and 2-Gd. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02337e Click here for additional data file. Click here for additional data file. Click here for additional data file.

PubMed Central

Fieser, Megan E.; Palumbo, Chad T.; La Pierre, Henry S.; Halter, Dominik P.; Voora, Vamsee K.; Ziller, Joseph W.

2017-01-01

A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3–, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures. PMID:29163894

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, D.; Waller, F.J.

1998-04-28

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Lithium Diisopropylamide-Mediated Reactions of Imines, Unsaturated Esters, Epoxides, and Aryl Carbamates: Influence of Hexamethylphosphoramide and Ethereal Cosolvents on Reaction Mechanisms

PubMed Central

Ma, Yun

2010-01-01

Several reactions mediated by lithium diisopropylamide (LDA) with added hex-amethylphosphoramide (HMPA) are described. The N-isopropylimine of cyclohex-anone lithiates via an ensemble of monomer-based pathways. Conjugate addition of LDA/HMPA to an unsaturated ester proceeds via di- and tetra-HMPA-solvated dimers. Deprotonation of norbornene epoxide by LDA/HMPA proceeds via an intermediate metalated epoxide as a mixed dimer with LDA. Ortholithiation of an aryl carbamate proceeds via a mono-HMPA-solvated monomer-based pathway. Dependencies on THF and other ethereal cosolvents suggest that secondary-shell solvation effects are important in some instances. The origins of the inordinate mechanistic complexity are discussed. PMID:17985891

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1996-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1994-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

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

NASA Astrophysics Data System (ADS)

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)).

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

PubMed

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.

First complete sauropod dinosaur skull from the Cretaceous of the Americas and the evolution of sauropod dentition.

PubMed

Chure, Daniel; Britt, Brooks B; Whitlock, John A; Wilson, Jeffrey A

2010-04-01

Sauropod dinosaur bones are common in Mesozoic terrestrial sediments, but sauropod skulls are exceedingly rare--cranial materials are known for less than one third of sauropod genera and even fewer are known from complete skulls. Here we describe the first complete sauropod skull from the Cretaceous of the Americas, Abydosaurus mcintoshi, n. gen., n. sp., known from 104.46 +/- 0.95 Ma (megannum) sediments from Dinosaur National Monument, USA. Abydosaurus shares close ancestry with Brachiosaurus, which appeared in the fossil record ca. 45 million years earlier and had substantially broader teeth. A survey of tooth shape in sauropodomorphs demonstrates that sauropods evolved broad crowns during the Early Jurassic but did not evolve narrow crowns until the Late Jurassic, when they occupied their greatest range of crown breadths. During the Cretaceous, brachiosaurids and other lineages independently underwent a marked diminution in tooth breadth, and before the latest Cretaceous broad-crowned sauropods were extinct on all continental landmasses. Differential survival and diversification of narrow-crowned sauropods in the Late Cretaceous appears to be a directed trend that was not correlated with changes in plant diversity or abundance, but may signal a shift towards elevated tooth replacement rates and high-wear dentition. Sauropods lacked many of the complex herbivorous adaptations present within contemporaneous ornithischian herbivores, such as beaks, cheeks, kinesis, and heterodonty. The spartan design of sauropod skulls may be related to their remarkably small size--sauropod skulls account for only 1/200th of total body volume compared to 1/30th body volume in ornithopod dinosaurs.

Biomechanical properties of polymer-infiltrated ceramic crowns on one-piece zirconia implants after long-term chewing simulation.

PubMed

Baumgart, Pia; Kirsten, Holger; Haak, Rainer; Olms, Constanze

2018-05-23

Implant and superstructure provide a complex system, which has to withstand oral conditions. Concerning the brittleness of many ceramics, fractures are a greatly feared issue. Therefore, polymer-infiltrated ceramic networks (PICNs) were developed. Because of its low Young's modulus and high elastic modulus, the PICN crown on a one-piece zirconia implant might absorb forces to prevent the system from fracturing in order to sustain oral forces. Recommendations for the material of superstructure on zirconia implants are lacking, and only one study investigates PICN crowns on these types of implants. Accordingly, this study aimed to examine PICN crowns on one-piece zirconia implants regarding bond strength and surface wear after long-term chewing simulation (CS). Twenty-five hybrid ceramic crowns (Vita Enamic, Vita Zahnfabrik) were produced using computer-aided design/computer-aided manufacturing (CAD/CAM) technology and adhesively bonded (RelyX™ Ultimate, 3M ESPE) to zirconia implants. Twenty of the specimens underwent simultaneous mechanical loading and thermocycling simulating a 5-year clinical situation (SD Mechatronik GmbH). Wear depth and wear volume, based on X-ray micro-computed tomography volume scans (Skyscan 1172-100-50, Bruker) before and after CS, were evaluated. All crowns were removed from the implants using a universal testing machine (Z010, Zwick GmbH&Co.KG). Subsequently, luting agent was light microscopically localized (Stemi 2000-C, Zeiss). With a scanning electron microscope (SEM, Phenom™ G2 pro, Phenom World), the area of abrasion was assessed. 1. After CS, none of the tested crowns were fractured or loosened. 2. The maximum vertical wear after CS was M = 0.31 ± 0.04 mm (mean ± standard deviation), and the surface wear was M = 0.74 ± 0.23 mm 3 . 3. The pull-off tests revealed a 1.8 times higher bond strength of the control group compared to the experimental group (t(23) = 8.69, p < 0.001). 4. Luting agent was mostly located in the crowns, not on the implants. 5. The area of abrasion showed avulsion and a rough surface. PICN on one-piece zirconia implants showed high bond strength and high wear after CS.

Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding.

PubMed

Hüttel, Wolfgang; Spencer, Jonathan B; Leadlay, Peter F

2014-01-01

Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD and O-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain of Streptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L(-1) dehydroxymonensin; ΔmonE: 0.50 g L(-1) demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L(-1) dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation.

Trans-ethyl methyl ether, the struggle for the detection of a complex molecule in hot cores

NASA Astrophysics Data System (ADS)

Fuchs, G. W.; Fuchs, U.; Giesen, T. F.; Wyrowski, F.

Many large and complex molecules of prebiotic importance have been found as constituents of interstellar clouds but their detection remains difficult and sometimes doubtful (Snyder et al. 2005). The complex spectrum of trans-ethyl methyl ether (EME) has been investigated in the laboratory (Fuchs et al. 2003) up to 350 GHz and is now known with high frequency precision, see Figure 1. In this work we present an extensive search for EME towards G34.26, NGC6334(I), Orion KL, SgrB2(N) and W51e2 in the 1 to 3 mm wavelength region. These sources have previously been shown to have a rich chemistry of complex molecules. The IRAM 30m telescope at Pico Veleta, Spain and the SEST 15m radio telescope in La Silla, Chile have been used for the observations. We looked at 5 - 11 frequency bands where EME has strong transitions. All sources were examined using long integration times up to 220 min (on+off), elevations greater 40◦ and under good weather conditions. For our analysis of the data we used the method of rotational-temperature-diagrams but also the myXCLASS (written by Peter Schilke) extension program to the GILDAS (Grenoble Image and Line Data Analysis Software) software which enabled us to simulate spectra of several molecules including their linewidth and intensities at the same time, see Figure 2. With this program a consistency check of molecular abundances and overall composition is possible even in dense spectra with many overlapping lines. The effect of the source size on the measured intensities has been considered and cross checks with other important molecules such as methanol, ethanol and di-methyl ether have been performed. Charnley et al. (2001) assigned one line in W51 e1/e2 and one line in Orion KL at 160.1 GHz, as well as a line in SgrB2(N) at 79.6 GHz to trans-ethyl methyl ether. From their isolated measurements, the column density of EME was estimated to be in the range 1014-1015 cm-2 in Sgr B2(N) corresponding to a fractional abundance of 10-10-10-9 and in the W51 region they estimate a fractional abundance of 10-10. However, our observations cannot confirm the tentative detection of EME in Orion KL within their given column density limits. There is evidence for the existence of the trans-ethyl methyl ether towards W51e2 with a column density of N=2×1014 cm-2 based on the detection of 14 lines which coincide with EME transition frequencies. We present new upper limits of 7-8×1013 cm-2 for the column densities of EME toward Orion KL, G34.26, NGC6334(I) and estimate the column density of SgrB2(N) to be of the same order. The W51e2 observations are discussed in more detail.

40 CFR 62.1104 - Identification of sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Section 62.1104 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS..., Contra Costa County Pulp Mill. (b) Louisiana Pacific Corp., Samoa Complex. (c) Crown Simpson Pulp Company, Fairhaven. (d) Simpson Paper Company, Shasta County Pulp Mill. [47 FR 47385, Oct. 26, 1982] Landfill Gas...

40 CFR 62.1104 - Identification of sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Section 62.1104 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS..., Contra Costa County Pulp Mill. (b) Louisiana Pacific Corp., Samoa Complex. (c) Crown Simpson Pulp Company, Fairhaven. (d) Simpson Paper Company, Shasta County Pulp Mill. [47 FR 47385, Oct. 26, 1982] Landfill Gas...

40 CFR 62.1104 - Identification of sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Section 62.1104 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS..., Contra Costa County Pulp Mill. (b) Louisiana Pacific Corp., Samoa Complex. (c) Crown Simpson Pulp Company, Fairhaven. (d) Simpson Paper Company, Shasta County Pulp Mill. [47 FR 47385, Oct. 26, 1982] Landfill Gas...

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Monomethyl Ether *Dimer Acids Dioxane Ethane Ethylene Glycol Monophenyl Ether *Ethoxylates, Misc. Ethylene Glycol Dimethyl Ether Ethylene Glycol Monobutyl Ether Ethylene Glycol Monoethyl Ether Ethylene Glycol...

Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals.

PubMed

Shaffer, Christopher J; Pepin, Robert; Tureček, František

2015-12-01

We report the first example of using ultraviolet (UV) photodissociation action spectroscopy for the investigation of gas-phase peptide cation-radicals produced by electron transfer dissociation. z-Type fragment ions (●) Gly-Gly-Lys(+), coordinated to 18-crown-6-ether (CE), are generated, selected by mass and photodissociated in the 200-400 nm region. The UVPD action spectra indicate the presence of valence-bond isomers differing in the position of the Cα radical defect, (α-Gly)-Gly-Lys(+) (CE), Gly-(α-Gly)-Lys(+) (CE) and Gly-Gly-(α-Lys(+))(CE). The isomers are readily distinguishable by UV absorption spectra obtained by time-dependent density functional theory (TD-DFT) calculations. In contrast, conformational isomers of these radical types are calculated to have similar UV spectra. UV photodissociation action spectroscopy represents a new tool for the investigation of transient intermediates of ion-electron reactions. Specifically, z-type cation radicals are shown to undergo spontaneous hydrogen atom migrations upon electron transfer dissociation. Copyright © 2015 John Wiley & Sons, Ltd.

Radical scavenging ability of some compounds isolated from Piper cubeba towards free radicals.

PubMed

Aboul-Enein, Hassan Y; Kładna, Aleksandra; Kruk, Irena

2011-01-01

The purpose of this study was to identify the antioxidant activity of 16 compounds isolated from Piper cubeba (CNCs) through the extent of their capacities to scavenge free radicals, hydroxyl radical (HO(•)), superoxide anion radical O•(2)(-) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), in different systems. Electron paramagnetic resonance (EPR) and 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, as the spin trap, and chemiluminescence techniques were applied. Using the Fenton-like reaction [Fe(II) + H(2)O(2)], CNCs were found to inhibit DMPO-OH radical formation ranging from 5 to 57% at 1.25 mmol L(-1) concentration. The examined CNCs also showed a high DPPH antiradical activity (ranging from 15 to 99% at 5 mmol L(-1) concentration). Furthermore, the results indicated that seven of the 16 tested compounds may catalyse the conversion of superoxide radicals generated in the potassium superoxide/18-crown-6 ether system, thus showing superoxide dismutase-like activity. The data obtained suggest that radical scavenging properties of CNCs might have potential application in many plant medicines. Copyright © 2010 John Wiley & Sons, Ltd.

Analysis of the morphology, stability, and folding pathways of ring polymers with supramolecular topological constraints using molecular simulation and nonlinear manifold learning

NASA Astrophysics Data System (ADS)

Wang, Jiang; Ferguson, Andrew

Ring polymers offer a wide range of natural and engineered functions and applications, including as circular bacterial DNA, crown ethers for cation chelation, and ``molecular machines'' such as mechanical nanoswitches. The morphology and dynamics of ring polymers are governed by the chemistry and degree of polymerization of the ring, and intramolecular and supramolecular topological constraints such as knots or mechanically-interlocked rings. We perform molecular dynamics simulations of polyethylene ring polymers as a function of degree of polymerization and in different topological states, including a knotted state, catenane state (two interlocked rings), and borromean state (three interlocked rings). Applying nonlinear manifold learning to our all-atom simulation trajectories, we extract low-dimensional free energy surfaces governing the accessible conformational states and their relative thermodynamic stability. The free energy surfaces reveal how degree of polymerization and topological constraints affect the thermally accessible conformations, chiral symmetry breaking, and folding and collapse pathways of the rings, and present a means to rationally engineer ring size and topology to preferentially stabilize particular conformational states.

Spatial and temporal trends in brominated flame retardants in seabirds from the Pacific coast of Canada.

PubMed

Miller, Aroha; Elliott, John E; Elliott, Kyle H; Guigueno, Mélanie F; Wilson, Laurie K; Lee, Sandi; Idrissi, Abde

2014-12-01

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) are bioaccumulative flame retardants. PBDEs increased in many ecosystems during the late 20th century, but recently have declined in some environments. To examine trends in the northern Pacific, we analysed PBDEs, HBCDD and carbon and nitrogen stable isotopes (δ13C and δ15N) to account for dietary effects in archived eggs of three seabird species from British Columbia, Canada, 1990-2011 (rhinoceros auklets, Cerorhinca monocerata; Leach's storm-petrels, Oceanodroma leucorhoa; ancient murrelets, Synthliboramphus antiquus, 2009 only). PBDEs increased until approximately 2000 and then decreased, while HBCDD increased exponentially throughout the examined period. No significant changes in dietary tracers were observed. HBCDD and ΣPBDE levels varied among species; ΣPBDE also varied among sites. Temporal changes in contaminant concentrations are unlikely to have been caused by dietary changes, and likely reflect the build-up followed by decreases associated with voluntary phase-outs and regulations implemented in North America to control PBDEs. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

Simple determination of fluoride in biological samples by headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry.

PubMed

Kwon, Sun-Myung; Shin, Ho-Sang

2015-08-14

A simple and convenient method to detect fluoride in biological samples was developed. This method was based on derivatization with 2-(bromomethyl)naphthalene, headspace solid phase microextraction (HS-SPME) in a vial, and gas chromatography-tandem mass spectrometric detection. The HS-SPME parameters were optimized as follows: selection of CAR/PDMS fiber, 0.5% 2-(bromomethyl)naphthalene, 250 mg/L 15-crown-5-ether as a phase transfer catalyst, extraction and derivatization temperature of 95 °C, heating time of 20 min and pH of 7.0. Under the established conditions, the lowest limits of detection were 9 and 11 μg/L in 1.0 ml of plasma and urine, respectively, and the intra- and inter-day relative standard deviation was less than 7.7% at concentrations of 0.1 and 1.0 mg/L. The calibration curve showed good linearity of plasma and urine with r=0.9990 and r=0.9992, respectively. This method is simple, amenable to automation and environmentally friendly. Copyright © 2015 Elsevier B.V. All rights reserved.

Metagenome Analyses of Corroded Concrete Wastewater Pipe Biofilms Reveals a Complex Microbial System

EPA Science Inventory

Analysis of whole-metagenome pyrosequencing data and 16S rRNA gene clone libraries was used to determine microbial composition and functional genes associated with biomass harvested from crown (top) and invert (bottom) sections of a corroded wastewater pipe. Taxonomic and functio...

Lignocellulose pretreatment in a fungus-cultivating termite

Treesearch

Hongjie Li; Daniel J. Yelle; Chang Li; Mengyi Yang; Jing Ke; Ruijuan Zhang; Yu Liu; Na Zhu; Shiyou Liang; Xiaochang Mo; John Ralph; Cameron R. Currie; Jianchu Mo

2017-01-01

Depolymerizing lignin, the complex phenolic polymer fortifying plant cell walls, is an essential but challenging starting point for the lignocellulosics industries. The variety of ether– and carbon–carbon interunit linkages produced via radical coupling during lignification limit chemical and biological depolymerization efficiency. In an ancient fungus-cultivating...

On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu

The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons.more » The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.« less

Cyclodextrin–polysaccharide-based, in situ-gelled system for ocular antifungal delivery

PubMed Central

Fernández-Ferreiro, Anxo; Fernández Bargiela, Noelia; Varela, María Santiago; Martínez, Maria Gil; Pardo, Maria; Piñeiro Ces, Antonio; Méndez, José Blanco; Barcia, Miguel González; Lamas, Maria Jesus

2014-01-01

Summary Fluconazole was studied with two different hydrophilic cyclodextrins (hydroxypropyl-β-cyclodextrin (HPBCD) and sulfobutyl ether-β-cyclodextrin (SBECD)) for the formation of inclusion complexes. HPBCD and SBECD showed low cell cytotoxicity in human keratocytes as assessed by the label-free xCELLigence system for real-time monitoring. The fluconazole–HPBCD complex was incorporated into an ion-sensitive ophthalmic gel composed of the natural polysaccharides gellan gum and κ-carrageenan. This system showed good bioadhesive properties and effective control of fluconazole release. PMID:25550757

[Quantitative assessment on artifacts of dental restorative materials in cone beam computed tomography].

PubMed

Yuan, Fu-song; Sun, Yu-chun; Xie, Xiao-yan; Wang, Yong; Lv, Pei-jun

2013-12-18

To quantitatively evaluate the artifacts appearance of eight kinds of common dental restorative materials, such as zirconia. For the full-crown tooth preparation of mandibular first molar, eight kinds of full-crowns, such as zirconia all-ceramic crown, glass ceramic crown, ceramage crown, Au-Pt based porcelain-fused-metal (PFM) crown, Pure Titanium PFM crown, Co-Cr PFM crown, Ni-Cr PFM crown, and Au-Pd metal crown were fabricated. And natural teeth in vitro were used as controls. These full-crown and natural teeth in vitro were mounted an ultraviolet-curable resin fixed plate. High resolution cone beam computed tomography (CBCT) was used to scan all of the crowns and natural teeth in vitro, and their DICOM data were imported into software MIMICS 10.0. Then, the number of stripes and the maximum diameters of artifacts around the full-crowns were evaluated quantitatively in two-dimensional tomography images. In the two-dimensional tomography images,the artifacts did not appear around the natural teeth in vitro, glass ceramic crown, and ceramage crown. But thr artifacts appeared around the zirconia all-ceramic and metal crown. The number of stripes of artifacts was five to nine per one crown. The maximum diameters of the artifacts were 2.4 to 2.6 cm and 2.2 to 2.7 cm. In the two-dimensional tomography images of CBCT, stripe-like and radical artifacts were caused around the zirconia all-ceramic crown and metal based porcelain-fused-metal crowns. These artifacts could lower the imaging quality of the full crown shape greatly. The artifact was not caused around the natural teeth in vitro, glass ceramic crown, and ceramage crown.

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

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 formation.

Assessment of thermal efficiency of heat recovery coke making

NASA Astrophysics Data System (ADS)

Tiwari, H. P.; Saxena, V. K.; Haldar, S. K.; Sriramoju, S. K.

2017-08-01

The heat recovery stamp charge coke making process is quite complicated due to the evolved volatile matter during coking, is partially combusted in oven crown and sole flue in a controlled manner to provide heat for producing metallurgical coke. Therefore, the control and efficient utilization of heat in the oven crown, and sole flue is difficult, which directly affects the operational efficiency. Considering the complexity and importance of thermal efficiency, evolution of different gases, combustion of gasses in oven crown and sole flue, and heating process of coke oven has been studied. A nonlinear regression methodology was used to predict temperature profile of different depth of coal cake during the coking. It was observed that the predicted temperature profile is in good agreement with the actual temperature profile (R2 = 0.98) and is validated with the actual temperature profile of other ovens. A complete study is being done to calculate the material balance, heat balance, and heat losses. This gives an overall understanding of heat flow which affects the heat penetration into the coal cake. The study confirms that 60% heat was utilized during coking.

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

PubMed

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

2018-06-01

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

Retention of veneered stainless steel crowns on replicated typodont primary incisors: an in vitro study.

PubMed

Guelmann, Marcio; Gehring, Daren F; Turner, Clara

2003-01-01

The purpose of this in vitro study was to determine the effect of crimping and cementation on retention of veneered stainless steel crowns. One hundred twenty crowns, 90 from 3 commercially available brands of veneered stainless steel crowns (Dura Crown, Kinder Krown, and NuSmile Primary Crown) and 30 (plain) Unitek stainless steel crowns were assessed for retention. An orthodontic wire was soldered perpendicular to the incisal edge of the crowns; the crowns were fitted to acrylic replicas of ideal crown preparations and were divided equally into 3 test groups: group 1--crowns were crimped only (no cement used); group 2--crowns were cemented only; and group 3--crowns were crimped and cemented to the acrylic replicas. An Instron machine recorded the amount of force necessary to dislodge the crowns and the results were statistically analyzed using 2-way ANOVA and Tukey honestly significant difference (HSD) test. Group 3 was statistically more retentive than groups 1 and 2. Group 2 was statistically more retentive than group 1 (P < .001). In group 1, Unitek crowns were statistically more retentive than the veneered crowns (P < .05). In group 2, NuSmile crowns showed statistically less retention values than all other crowns (P < .05). In group 3,Kinder Krown crowns showed statistically better retention rates than all other brands (P < .05). Significantly higher retention values were obtained for all brands tested when crimping and cement were combined. The crowns with veneer facings were significantly more retentive than the nonveneered ones when cement and crimping were combined.

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

PubMed

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).

Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

PubMed

Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

2010-06-01

To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Phillips Petroleum Co. is poised to license its high conversion process to produce fuel ethers for blending in reformulated gasolines. The technology has been proven in a Phillips semiworks at Bartlesville, Okla. The process can produce methyl tertiary butyl ether, ethyl tertiary butyl ether, tertiary amyl methyl ether, or tertiary amyl ethyl ether with typical refinery process equipment and techniques. Phillips said it can achieve conversion levels of 92-99%, depending on the ether. The ether produced is determined by which hydrocarbon fraction is used for feedstock and which alcohol is chosen for reaction. The process is described.

A new route to synthesize aryl acetates from carbonylation of aryl methyl ethers

PubMed Central

Yang, Youdi; Li, Shaopeng; Han, Buxing

2018-01-01

Ether bond activation is very interesting because the synthesis of many valuable compounds involves conversion of ethers. Moreover, C–O bond cleavage is also very important for the transformation of biomass, especially lignin, which abundantly contains ether bonds. Developing efficient methods to activate aromatic ether bonds has attracted much attention. However, this is a challenge because of the inertness of aryl ether bonds. We proposed a new route to activate aryl methyl ether bonds and synthesize aryl acetates by carbonylation of aryl methyl ethers. The reaction could proceed over RhCl3 in the presence of LiI and LiBF4, and moderate to high yields of aryl acetates could be obtained from transformation of various aryl methyl ethers with different substituents. It was found that LiBF4 could assist LiI to cleave aryl methyl ether bonds effectively. The reaction mechanism was proposed by a combination of experimental and theoretical studies. PMID:29795781

Implant materials generate different peri-implant inflammatory factors: poly-ether-ether-ketone promotes fibrosis and microtextured titanium promotes osteogenic factors.

PubMed

Olivares-Navarrete, Rene; Hyzy, Sharon L; Slosar, Paul J; Schneider, Jennifer M; Schwartz, Zvi; Boyan, Barbara D

2015-03-15

An in vitro study examining factors produced by human mesenchymal stem cells on spine implant materials. The aim of this study was to examine whether the inflammatory microenvironment generated by cells on titanium-aluminum-vanadium (Ti-alloy, TiAlV) surfaces is affected by surface microtexture and whether it differs from that generated on poly-ether-ether-ketone (PEEK). Histologically, implants fabricated from PEEK have a fibrous connective tissue surface interface whereas Ti-alloy implants demonstrate close approximation with surrounding bone. Ti-alloy surfaces with complex micron/submicron scale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation whereas PEEK favors fibrous tissue formation. Human mesenchymal stem cells were cultured on tissue culture polystyrene, PEEK, smooth TiAlV, or macro-/micro-/nano-textured rough TiAlV (mmnTiAlV) disks. Osteoblastic differentiation and secreted inflammatory interleukins were assessed after 7 days. Fold changes in mRNAs for inflammation, necrosis, DNA damage, or apoptosis with respect to tissue culture polystyrene were measured by low-density polymerase chain reaction array. Data were analyzed by analysis of variance, followed by Bonferroni's correction of Student's t-test. Cells on PEEK upregulated mRNAs for chemokine ligand-2, interleukin (IL) 1β, IL6, IL8, and tumor necrosis factor. Cells grown on the mmnTiAlV had an 8-fold reduction in mRNAs for toll-like receptor-4. Cells grown on mmnTiAlV had reduced levels of proinflammatory interleukins. Cells on PEEK had higher mRNAs for factors strongly associated with cell death/apoptosis, whereas cells on mmnTiAlV exhibited reduced cytokine factor levels. All results were significant (P < 0.05). These results suggest that fibrous tissue around PEEK implants may be due to several factors: reduced osteoblastic differentiation of progenitor cells and production of an inflammatory environment that favors cell death via apoptosis and necrosis. Ti alloy surfaces with complex macro/micro/nanoscale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation. N/A.

Comparison of the arithmetic and geometric means in estimating crown diameter and crown cross-sectional area

Treesearch

KaDonna Randolph

2010-01-01

The use of the geometric and arithmetic means for estimating tree crown diameter and crown cross-sectional area were examined for trees with crown width measurements taken at the widest point of the crown and perpendicular to the widest point of the crown. The average difference between the geometric and arithmetic mean crown diameters was less than 0.2 ft in absolute...

Catalytic oxidation of dimethyl ether

DOEpatents

Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

2016-05-10

A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

Modeling of contact theories for the manipulation of biological micro/nanoparticles in the form of circular crowned rollers based on the atomic force microscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korayem, M. H.; Khaksar, H.; Taheri, M.

2013-11-14

This article has dealt with the development and modeling of various contact theories for biological nanoparticles shaped as cylinders and circular crowned rollers for application in the manipulation of different biological micro/nanoparticles based on Atomic Force Microscope. First, the effective contact forces were simulated, and their impact on contact mechanics simulation was investigated. In the next step, the Hertz contact model was simulated and compared for gold and DNA nanoparticles with the three types of spherical, cylindrical, and circular crowned roller type contact geometries. Then by reducing the length of the cylindrical section in the circular crowned roller geometry, themore » geometry of the body was made to approach that of a sphere, and the results were compared for DNA nanoparticles. To anticipatory validate the developed theories, the results of the cylindrical and the circular crowned roller contacts were compared with the results of the existing spherical contact simulations. Following the development of these contact models for the manipulation of various biological micro/nanoparticles, the cylindrical and the circular crowned roller type contact theories were modeled based on the theories of Lundberg, Dowson, Nikpur, Heoprich, and Hertz for the manipulation of biological micro/nanoparticles. Then, for a more accurate validation, the results obtained from the simulations were compared with those obtained by the finite element method and with the experimental results available in previous articles. The previous research works on the simulation of nanomanipulation have mainly investigated the contact theories used in the manipulation of spherical micro/nanoparticles. However since in real biomanipulation situations, biological micro/nanoparticles of more complex shapes need to be displaced in biological environments, this article therefore has modeled and compared, for the first time, different contact theories for use in the biomanipulation of cylindrical and circular crowned roller shaped micro/nanoparticles. The results of models indicate that the contact model of Hertz achieves the largest amount of deformation for the DNA nanoparticle in cylindrical form and the contact model of Heoprich achieves the largest deformation for the circular crowned roller shaped DNA. Of course, this finding is not always true for the other nanoparticles; and considering the mechanical and environmental characteristics, different results can be obtained. Also, by comparing the deformations of different types of nanoparticles, it was determined that the platelet type nanoparticles display the highest degree of deformation in all the considered models, due to their particular mechanical characteristics.« less

Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding

PubMed Central

Spencer, Jonathan B; Leadlay, Peter F

2014-01-01

Summary Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD and O-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain of Streptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L−1 dehydroxymonensin; ΔmonE: 0.50 g L−1 demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L−1 dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation. PMID:24605157

Fourier transform C-13 NMR analysis of some free and potassium-ion complexed antibiotics.

NASA Technical Reports Server (NTRS)

Ohnishi, M.; Fedarko, M.-C.; Baldeschwieler, J. D.; Johnson, L. F.

1972-01-01

Fourier transforms of the noise-decoupled, natural abundance C-13 NMR free induction decays of the cyclic antibiotic valinomycin and its potassium-ion complex have been obtained at 25.2 MHz. Comparisons are made with C-13 NMR spectra taken at 22.6 MHz of the cyclic antibiotic nonactin and the synthetic polyether dicyclohexyl-18-crown-6 and their potassium complexes. The results obtained suggest that conformational rearrangements of the molecule as a whole can compete with direct interactions between carbons and the potassium ion in determining C-13 chemical shift differences between the free and complexed species.

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.

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.

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)

EPA Science Inventory

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...

The Ether-Cleaving Methyltransferase System of the Strict Anaerobe Acetobacterium dehalogenans: Analysis and Expression of the Encoding Genes▿

PubMed Central

Schilhabel, Anke; Studenik, Sandra; Vödisch, Martin; Kreher, Sandra; Schlott, Bernhard; Pierik, Antonio Y.; Diekert, Gabriele

2009-01-01

Anaerobic O-demethylases are inducible multicomponent enzymes which mediate the cleavage of the ether bond of phenyl methyl ethers and the transfer of the methyl group to tetrahydrofolate. The genes of all components (methyltransferases I and II, CP, and activating enzyme [AE]) of the vanillate- and veratrol-O-demethylases of Acetobacterium dehalogenans were sequenced and analyzed. In A. dehalogenans, the genes for methyltransferase I, CP, and methyltransferase II of both O-demethylases are clustered. The single-copy gene for AE is not included in the O-demethylase gene clusters. It was found that AE grouped with COG3894 proteins, the function of which was unknown so far. Genes encoding COG3894 proteins with 20 to 41% amino acid sequence identity with AE are present in numerous genomes of anaerobic microorganisms. Inspection of the domain structure and genetic context of these orthologs predicts that these are also reductive activases for corrinoid enzymes (RACEs), such as carbon monoxide dehydrogenase/acetyl coenzyme A synthases or anaerobic methyltransferases. The genes encoding the O-demethylase components were heterologously expressed with a C-terminal Strep-tag in Escherichia coli, and the recombinant proteins methyltransferase I, CP, and AE were characterized. Gel shift experiments showed that the AE comigrated with the CP. The formation of other protein complexes with the O-demethylase components was not observed under the conditions used. The results point to a strong interaction of the AE with the CP. This is the first report on the functional heterologous expression of acetogenic phenyl methyl ether-cleaving O-demethylases. PMID:19011025

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

PubMed

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.

NIOSH Manual of Analytical Methods (third edition). Fourth supplement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1990-08-15

The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

Lewis base activation of Lewis acids: catalytic, enantioselective addition of silyl ketene acetals to aldehydes.

PubMed

Denmark, Scott E; Beutner, Gregory L; Wynn, Thomas; Eastgate, Martin D

2005-03-23

The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent catalyst for the aldol addition of acetate-, propanoate-, and isobutyrate-derived silyl ketene acetals to conjugated and nonconjugated aldehydes. Furthermore, vinylogous aldol reactions of silyl dienol ethers are also demonstrated. The high levels of regio-, anti diastereo-, and enantioselectivity observed in these reactions can be rationalized through consideration of an open transition structure where steric interactions between the silyl cation complex and the approaching nucleophile are dominant.

Lithium diffusion in polyether ether ketone and polyimide stimulated by in situ electron irradiation and studied by the neutron depth profiling method

NASA Astrophysics Data System (ADS)

Vacik, J.; Hnatowicz, V.; Attar, F. M. D.; Mathakari, N. L.; Dahiwale, S. S.; Dhole, S. D.; Bhoraskar, V. N.

2014-10-01

Diffusion of lithium from a LiCl aqueous solution into polyether ether ketone (PEEK) and polyimide (PI) assisted by in situ irradiation with 6.5 MeV electrons was studied by the neutron depth profiling method. The number of the Li atoms was found to be roughly proportional to the diffusion time. Regardless of the diffusion time, the measured depth profiles in PEEK exhibit a nearly exponential form, indicating achievement of a steady-state phase of a diffusion-reaction process specified in the text. The form of the profiles in PI is more complex and it depends strongly on the diffusion time. For the longer diffusion time, the profile consists of near-surface bell-shaped part due to Fickian-like diffusion and deeper exponential part.

Repairing a Facial Cleft by Polyether-Ether-Ketone Implant Combined With Titanium Mesh.

PubMed

Deng, Yuan; Tang, Weiwei; Li, Zhengkang

2018-05-15

The Tessier Number 4 cleft is one of the rarest, most complex craniofacial anomalies that presents difficulties in surgical treatment. In this article, we report a case of simultaneous facial depression, eye displacement, and medial canthus deformity. In this case, the maxillary bony defect was reconstructed using computer-assisted design computer-assisted manufacturing (CAD-CAM) polyether-ether-ketone (PEEK) material, and the orbital floor defect was repaired with AO prefabricated titanium mesh. Additionally, the medial canthus was modified with canthopexy and a single Z-plasty flap. Owing to its relative rarity and varied clinical presentations, no definitive operative methods have been accepted for Tessier No. 4 facial cleft. This study presents the combination of CAD-CAM manufactured PEEK material and titanium mesh as an alternative approach for reconstructing the bony defect of Tessier No. 4 facial clefts.

[Preliminary evaluation of plastic crown restoration supported by osseointegrated implants].

PubMed

Huang, J; Zhang, K

1997-08-01

This study was to evaluate the feasibility of plastic crown restoration supported by osseointegrated implants. The following conclusions were drawn from this study: plastic crown gave better biomechanical consideration than porcelain fused to metal (PFM) crown in osseointegrated prostheses, but plastic crown gave worse wearability, tensile strength, compression strength and flexuaral strength than PFM crown. After restoration the disadvantages of the plastic crown were beyond the clinical acceptable range. It showed plastic crown designed dental prothetic implantation was unfeasible.

HPLC-Based Mass Spectrometry Characterizes the Phospholipid Alterations in Ether-Linked Lipid Deficiency Models Following Oxidative Stress

PubMed Central

Drechsler, Robin; Chen, Shaw-Wen; Dancy, Blair C. R.; Mehrabkhani, Lena

2016-01-01

Despite the fact that the discovery of ether-linked phospholipids occurred nearly a century ago, many unanswered questions remain concerning these unique lipids. Here, we characterize the ether-linked lipids of the nematode with HPLC-MS/MS and find that more than half of the phosphoethanolamine-containing lipids are ether-linked, a distribution similar to that found in mammalian membranes. To explore the biological role of ether lipids in vivo, we target fatty acyl-CoA reductase (fard-1), an essential enzyme in ether lipid synthesis, with two distinct RNAi strategies. First, when fard-1 RNAi is initiated at the start of development, the treated animals have severely reduced ether lipid abundance, resulting in a shift in the phosphatidylethanolamine lipid population to include more saturated fatty acid chains. Thus, the absence of ether lipids during development drives a significant remodeling of the membrane landscape. A later initiation of fard-1 RNAi in adulthood results in a dramatic reduction of new ether lipid synthesis as quantified with 15N-tracers; however, there is only a slight decrease in total ether lipid abundance with this adult-only fard-1 RNAi. The two RNAi strategies permit the examination of synthesis and ether lipid abundance to reveal a relationship between the amount of ether lipids and stress survival. We tested whether these species function as sacrificial antioxidants by directly examining the phospholipid population with HPLC-MS/MS after oxidative stress treatment. While there are significant changes in other phospholipids, including polyunsaturated fatty acid-containing species, we did not find any change in ether-linked lipids, suggesting that the role of ether lipids in stress resistance is not through their general consumption as free radical sinks. Our work shows that the nematode will be a useful model for future interrogation of ether lipid biosynthesis and the characterization of phospholipid changes in various stress conditions. PMID:27893806

The Complexation of the Na(super +) by 18-Crown-6 Studied via Nuclear Magnetic Resonance

ERIC Educational Resources Information Center

Peters, Steven J.; Stevenson, Cheryl D.

2004-01-01

A student friendly experiment that teaches several important concepts of modern nuclear magnetic resonance (NMR), like multinuclear capabilities, the NMR time scale, and time-averaged signals, is described along with some important concepts of thermo chemical equilibria. The mentioned experiment involves safe and inexpensive compounds, such as…

Spruce beetle-induced changes to Engelmann spruce foliage flammability

Treesearch

Wesley G. Page; Michael J. Jenkins; Justin B. Runyon

2014-01-01

Intermountain Engelmann spruce (Picea engelmannii Parry ex Engelm) stands affected by the spruce beetle (Dendroctonus rufipennis Kirby) represent a unique and growing fuel complex. In this study, we quantified and compared the changes in moisture content, chemistry, and flammability of foliage from trees in three crown condition classes: unattacked (green [G]),...

DFT calculation and experimental validation on the interactions of bis(trifluoromethylsulfonyl)imide and hexafluorophosphate with cesium

NASA Astrophysics Data System (ADS)

Sun, Taoxiang; Duan, Wuhua; Wang, Yaxing; Hu, Shaowen; Wang, Shuao; Chen, Jing; Shen, Xinghai

2017-11-01

Bis(trifluoromethylsulfonyl)imide (NTf2-) and hexafluorophosphate (PF6-) are the most frequently used anions for hydrophobic ionic liquids (ILs) which have been considered as promising solvents in the extraction of cesium ions. The interactions of NTf2- and PF6- with Cs+ were explored in this work. The results of DFT calculation indicated that both Cs+ and Cs(18C6)+ prefer to interact with two NTf2- or PF6- anions in gas phase, where 18C6 is 18-crown-6. The complex of Cs(NTf2)2- was observed in electrospray ionization mass spectrometry (ESI-MS), and the complexes of [Cs(18C6)NTf2]2 and [Cs(18C6)PF6]2 were crystallized in which Cs(18C6)+ interacted with two anions. The interactions of NTf2- with cesium resulted in a synergistic effect between dicyclohexano-18-crown-6 (DCH18C6) and NTf2- in the extraction of Cs+ using n-octanol as diluent. However, DFT calculation revealed that the complex Cs(DCH18C6)+ interacted with one NTf2- anion was more thermodynamically stable than that with two anions in organic phase, different from that in gas phase.

Double keystone bird in a keystone species complex.

PubMed

Daily, G C; Ehrlich, P R; Haddad, N M

1993-01-15

Species in a Colorado subalpine ecosystem show subtle interdependences. Red-naped sapsuckers play two distinct keystone roles. They excavate nest cavities in fungus-infected aspens that are required as nest sites by two species of swallows, and they drill sap wells into willows that provide abundant nourishment for themselves, hummingbirds, orange-crowned warblers, chipmunks, and an array of other sap robbers. The swallows thus depend on, and the sap robbers benefit from, a keystone species complex comprised of sapsuckers, willows, aspens, and a heartwood fungus. Disappearance of any element of the complex could cause an unanticipated unraveling of the community.

Combination of three metals for the treatment of cancer: gallium, rhenium and platinum. 1. Determination of the optimal schedule of treatment.

PubMed

Collery, Philippe; Mohsen, Ahmed; Kermagoret, Anthony; D'Angelo, Jean; Morgant, Georges; Desmaele, Didier; Tomas, Alain; Collery, Thomas; Wei, Ming; Badawi, Abdelfattah

2012-07-01

Platinum is well known for its anticancer activity, firstly used as cis-diaminedichloroplatinum (II) (CDDP), with a wide range of activity. Its main mechanism of action involves its binding to DNA. Gallium, another metal, has also demonstrated apoptotic effects on malignant cells, but through interaction with targets other than DNA, such as the membrane, cytoskeleton and proteasome, and on enzyme activities. An antitumor synergism between CDDP and both gallium and rhenium compounds has been demonstrated. For these reasons, we proposed to combine these three metals and to determine at which doses each compound could be administered without major toxicity. CDDP, tetrakis(1-octanol) tris(5-aminosalicylate)gallium(III), and a diseleno-ether rhenium(I) complex were used in this experimental study in breast cancer MCF-7 tumor-bearing mice. CDDP was administered intraperitoneally (i.p.) twice a week at the dose of 3 mg/kg. Tetrakis(1-octanol) tris(5-aminosalicylate) gallium (III) and rhenium(I) diseleno-ether complexes were administered orally, daily, five days a week for three weeks, at doses ranging from 20 to 100 mg/kg for the gallium compound and from 10 to 50 mg/kg for the rhenium compound. Doses of 10 mg/kg of rhenium(I) diseleno-ether, and 100 mg/kg of the salicylate gallium compound, in combination with CDDP induced a significant decrease of 50% of the tumor volume, by comparison with the control group. In contrast, the decrease of the tumor volume in mice treated by CDDP alone was less than 25%. Changes in the sequence of administration of the three metals will be discussed to improve the therapeutic index.

Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

PubMed

Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

2017-06-15

Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

Estimating the weight of crown segments for old-growth Douglas-fir and western hemlock.

Treesearch

J.A. Kendall Snell; Timothy A. Max

1985-01-01

The purpose of this study was to develop and validate estimators to predict total crown weight and weight of any segment of crown for old-growth felled and bucked Douglas-fir and western hemlock trees. Equations were developed for predicting weight of continuous live crown, total live crown, dead crown, any segment of live crown, and individual branches for old-growth...

Crown Position and Light Exposure Classification-An Alternative to Field-Assigned Crown Class

Treesearch

William A. Bechtold

2003-01-01

Crown class, an ordinal tree-level mensuration attribute used extensively by foresters, is difficult to assign in the field because definitions of individual classes are confounded by ambiguous references to the position the tree in the canopy and amount of light received by its crown. When crown class is decomposed into its two elements-crown position and crown light...

Frequency and variability of dental morphology in deciduous and permanent dentition of a Nasa indigenous group in the municipality of Morales, Cauca, Colombia.

PubMed

Díaz, Eider; García, Lorena; Hernández, Michelle; Palacio, Lesly; Ruiz, Diana; Velandia, Nataly; Villavicencio, Judy; Moreno, Freddy

2014-01-01

To determine the frequency, variability, sexual dimorphism and bilateral symmetry of fourteen dental crown traits in the deciduous and permanent dentition of 60 dental models (35 women and 25 men) obtained from a native, indigenous group of Nasa school children of the Musse Ukue group in the municipality of Morales, Department of Cauca, Colombia. This is a quantitative, descriptive, cross-sectional study that characterizes dental morphology by means of the systems for temporary dentition from Dahlberg (winging), and ASUDAS (crowding, reduction of hypocone, metaconule and cusp 6), Hanihara (central and lateral incisors in shovel-shape and cusp 7), Sciulli (double bit, layered fold protostylid, cusp pattern and cusp number) and Grine (Carabelli trait); and in permanent dentition from ASUDAS (Winging, crowding, central and lateral incisors in shovel-shape and double shovel-shape, Carabelli trait, hypocone reduction, metaconule, cusp pattern, cusp number, layered fold protostylid, cusp 6 and cusp 7). The most frequent dental crown features were the shovel-shaped form, grooved and fossa forms of the Carabelli trait, metaconule, cusp pattern Y6, layered fold, protostylid (point P) and cusp 6. Sexual dimorphism was not observed and there was bilateral symmetry in the expression of these features. The sample studied presented a great affinity with ethnic groups belonging to the Mongoloid Dental Complex due to the frequency (expression) and variability (gradation) of the tooth crown traits, upper incisors, the Carabelli trait, the protostylid, cusp 6 and cusp 7. The influence of the Caucasoide Dental Complex associated with ethno-historical processes cannot be ruled out.

Preformed posterior stainless steel crowns: an update.

PubMed

Croll, T P

1999-02-01

For almost 50 years, dentists have used stainless steel crowns for primary and permanent posterior teeth. No other type of restoration offers the convenience, low cost, durability, and reliability of such crowns when interim full-coronal coverage is required. Preformed stainless steel crowns have improved over the years. Better luting cements have been developed and different methods of crown manipulation have evolved. This article reviews stainless steel crown procedures for primary and permanent posterior teeth. Step-by-step placement of a primary molar stainless steel crown is documented and permanent molar stainless steel crown restoration is described. A method for repairing a worn-through crown also is reviewed.

Deformation of crowns during cementation.

PubMed

Wilson, P R; Goodkind, R J; Delong, R; Sakaguchi, R

1990-11-01

Deformation of crowns during cementation was investigated by a simple loading system of defined crowns with silicone fluids as cements. Deformation of the crowns was measured by long stain gauges that encircled the cervical margins. Die spacing was simulated by etching the die. Venting was simulated by removing a small screw. Deformation of the crowns was decreased by decreasing the viscosity of fluid, increasing the thickness of the crowns, and venting. Etching the die decreased the seating times of the crowns, but did not alter the level of deformation. Terminal cementation with zinc phosphate cement confirmed the presence of crown deformation during cementation. The results have consequences for bonded and all-ceramic crowns, and explain several clinical phenomena. It is suggested that low viscosity cements, low seating forces, and die spacing be used to decrease the deformation of crowns during seating. The importance of passive fitting of the crown to the tooth is stressed.

Di-μ-bromido-bis-[(diethyl ether-κO)(2,4,6-tri-methyl-phen-yl)magnesium]: the mesityl Grignard reagent.

PubMed

Seven, Omer; Bolte, Michael; Lerner, Hans-Wolfram

2013-01-01

The crystal structure of the title compound, [Mg2Br2(C9H11)2(C4H10O)2], features a centrosymmetric two-centre magnesium complex with half a mol-ecule in the asymmetric unit. The Mg atom is in a considerably distorted Br2CO coordination. Bond lengths and angles are comparable with already published values. The crystal packing is stabilized by C-H⋯π inter-actions linking the complexes into sheets parallel to (0-11).

Intramolecular Hydrogen Transfer Reactions Catalyzed by Pentamethylcyclopentadienyl Rhodium and Cobalt Olefin Complexes: Mechanistic Studies.

PubMed

Bolig, Andrew D; Lyons, Thomas W; DiSalvo, Darren T; Brookhart, Maurice

2016-01-08

The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp * M(VTMS) 2 ] ( 1 , M=Rh, 2 , M=Co, Cp* = C 5 Me 5 , VTMS = vinyltrimethylsilane) complexes has been studied using vinyl silane protected alcohols as substrates. Deuterium-labeled substrates have been synthesized and the regioselectivity of H/D transfers investigated using 1 H and 2 H NMR spectroscopy. The labeling studies establish a regioselective pathway consisting of alkene directed α C-H activation, 2,1 alkene insertion, and finally β-hydride elimination to give silyl enol ether products.

Nickel(0)-Catalyzed Inert C-O Bond Functionalization: Organo Rare-Earth Metal Complex as the Coupling Partner.

PubMed

Yan, Xiangqian; Yang, Fanzhi; Cai, Guilong; Meng, Qingwei; Li, Xiaofang

2018-02-02

An organo rare-earth metal complex has been employed as a highly efficient nucleophile in Ni(0)-catalyzed C-O bond functionalization. The optimized catalytic system which consists of Ni(cod) 2 , PCy 3 , and t-BuONa could smoothly convert 1 equiv of naphthyl ethers to alkylated naphthalene analogues with 0.4 equiv of Ln(CH 2 SiMe 3 ) 3 (THF) 2 , delivering good to excellent yields. The reaction system could also activate the ArCH 2 -O bond with mild base.

Review of Recent Developments on Using an Off-Lattice Monte Carlo Approach to Predict the Effective Thermal Conductivity of Composite Systems with Complex Structures

PubMed Central

Gong, Feng; Duong, Hai M.; Papavassiliou, Dimitrios V.

2016-01-01

Here, we present a review of recent developments for an off-lattice Monte Carlo approach used to investigate the thermal transport properties of multiphase composites with complex structure. The thermal energy was quantified by a large number of randomly moving thermal walkers. Different modes of heat conduction were modeled in appropriate ways. The diffusive heat conduction in the polymer matrix was modeled with random Brownian motion of thermal walkers within the polymer, and the ballistic heat transfer within the carbon nanotubes (CNTs) was modeled by assigning infinite speed of thermal walkers in the CNTs. Three case studies were conducted to validate the developed approach, including three-phase single-walled CNTs/tungsten disulfide (WS2)/(poly(ether ether ketone) (PEEK) composites, single-walled CNT/WS2/PEEK composites with the CNTs clustered in bundles, and complex graphene/poly(methyl methacrylate) (PMMA) composites. In all cases, resistance to heat transfer due to nanoscale phenomena was also modeled. By quantitatively studying the influencing factors on the thermal transport properties of the multiphase composites, it was found that the orientation, aggregation and morphology of fillers, as well as the interfacial thermal resistance at filler-matrix interfaces would limit the transfer of heat in the composites. These quantitative findings may be applied in the design and synthesis of multiphase composites with specific thermal transport properties. PMID:28335270

Constraining the Molecular Complexity in the Interstellar Medium—The Formation of Ethyl Methyl Ether (CH3OCH2CH3) in Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Frigge, Robert; Kaiser, Ralf I.

2018-05-01

We report the first confirmed synthesis of ethyl methyl ether (EME, CH3CH2OCH3) within astrophysical model ices containing water (H2O) and methane (CH4) exposed to ionizing radiation at ultra-low temperatures of 5 K. EME (also known as methoxyethane), was recently observed toward Orion KL and currently is the largest confirmed oxygen-bearing molecule found in the interstellar medium. Exploiting isomer-selective photoionization (PI) of the subliming molecules in the temperature-programmed desorption phase at 10.49, 9.92, and 9.70 eV, coupled with reflectron time-of-flight mass spectrometry and isotopic substitution experiments (H2 18O–CH4), the detection of fragment ions of EME at m/z = 45 (C2H5O+) and m/z = 59 (C3H7O+), and probing the proton transfer in subliming ethanol–EME complexes via m/z = 61 (C3H9O+), the present study reveals that EME can be formed from suprathermal reactions initiated by cosmic rays and secondary electrons generated within astrophysical ices. The detection of EME in our experiments represents a significant advance in the understanding of formation pathways of complex organic molecules present in hot cores and helps to constrain astrochemical models on the formation of such species within molecular clouds.

The use of functionally graded dental crowns to improve biocompatibility: a finite element analysis.

PubMed

Mahmoudi, Mojtaba; Saidi, Ali Reza; Hashemipour, Maryam Alsadat; Amini, Parviz

2018-02-01

In post-core crown restorations, the significant mismatch between stiffness of artificial crowns and dental tissues leads to stress concentration at the interfaces. The aim of the present study was to reduce the destructive stresses by using a class of inhomogeneous materials called functionally graded materials (FGMs). For the purpose of the study, a 3-dimentional computer model of a premolar tooth and its surrounding tissues were generated. A post-core crown restoration with various crown materials, homogenous and FGM materials, were simulated and analyzed by finite element method. Finite element and statistical analysis showed that, in case of oblique loading, a significant difference (p < 0.05) was found at the maximum von Mises stresses of the crown margin between FGM and homogeneous crowns. The maximum von Mises stresses of the crown margin generated by FGM crowns were lower than those generated by homogenous crowns (70.8 vs. 46.3 MPa) and alumina crown resulted in the highest von Mises stress at the crown margin (77.7 MPa). Crown materials of high modulus of elasticity produced high stresses at the cervical region. FGM crowns may reduce the stress concentration at the cervical margins and consequently reduce the possibility of fracture.

Biomechanical evaluation of the natural abutment teeth in combined tooth-implant-supported telescopic prostheses: a three-dimensional finite element analysis.

PubMed

Chen, Yu; Wang, Chao; Huang, Yuanding; Feng, Tianming; Zou, Huawei; Fan, Yubo

2017-07-01

Telescopic overdentures supported by the combination of natural teeth and implants have been thought a valuable treatment for the severely compromised partially edentulous patients. But the combination of teeth and implants involves highly complex biomechanical problems. This study is to evaluate biomechanical behaviors of the natural abutment teeth with the treatment of combined tooth-implant supported telescopic crown prostheses in mandible through 3D FEA. According to this study, the prosthetic option supported by a combination of teeth and implants and retained by double crowns could protect teeth and their periodontal support tissues acting as a rigid splint, and may be a valuable treatment option for partially edentulous patients with severely reduced remaining teeth in mandible.

Boundary lubrication, thermal and oxidative stability of a fluorinated polyether and a perfluoropolyether triazine

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Snyder, C. E., Jr.

1979-01-01

Boundary lubricating characteristics, thermal stability, and oxidation-corrosion stability were determined for a fluorinated polyether and a perfluoropolyether triazine. A ball-on-disk apparatus, a tensimeter, and oxidation-corrosion apparatus were used. Results were compared to data for a polyphenyl ether and a C-ether. The polyether and triazine yielded better boundary lubricating characteristics than either the polyphenyl ether or C-ether. The polyphenyl ether had the greatest thermal stability (443 C) while the other fluids had stabilities in the range 389 to 397 C. Oxidation-corrosion results indicated the following order of stabilities: perfluoropolyether trizine greater than polyphenyl ether greater than C-ether greater than fluorinated polyether.

Tracking forest canopy dynamics from an automated proximal hyperspectral monitoring system: linking remote sensing observations to leaf level photosynthetic processes

NASA Astrophysics Data System (ADS)

Woodgate, W.; van Gorsel, E.; Hughes, D.; Suarez, L.; Cabello-Leblic, A.; Held, A. A.; Norton, A.; Dempsey, R.

2017-12-01

To better understand the vegetation response to climate extremes we have developed a fully automated hyperspectral and thermal monitoring system installed on a flux tower at a mature Eucalypt forest site - Tumbarumba, Australia. The automated system bridges spatial, spectral and temporal scales between satellite and in situ observations. Here, we have been acquiring high resolution panoramic hyperspectral and thermal images of the forest canopy three times per day since mid-2014.A specific focus of the work to date has been linking light use efficiency (LUE) as measured by the flux tower to remote sensing observations from the leaf, to crown, to canopy scale. Specifically, targeted field campaigns were conducted in 2016 to establish the interrelationship between structure, function, and spectra. At the leaf level destructive sampling to quantify photosynthetic pigments was conducted to pick apart the mechanisms contributing to photosynthetic processes of non-photochemical quenching and the resultant changes in observed leaf spectra. At the crown level, Terrestrial Laser Scanning data was used to derive canopy structural information, enabling distance to crown and crown foliage density to be calculated to a fine degree of detail. This information is critical for correcting attenuation of the thermal signal from atmospheric transmission, and to distinguish the relative foliage-to-soil contribution to the thermal and hyperspectral imagery. Ancillary data streams from sap flow and dendrometer devices serve to link leaf, crown and canopy observations.Preliminary results of the leaf and crown level relationships between function and spectra will be discussed. We will demonstrate that operating in a tall canopy (40m) forest can lead to additional complexities. We have found the relationship strength between traditional remote sensing LUE proxies and photosynthetic proxies derived from pigments varies strongly with canopy height and pigment pool size. Additionally, the significance of the relationship between some leaf pigments and spectra hinged upon the inclusion of juvenile or unhealthy leaf samples, which were not representative of the canopy. This has implications for temporal scaling of remote sensing proxies from diurnal to seasonal time frames.

Effect of increased crown height on stress distribution in short dental implant components and their surrounding bone: A finite element analysis.

PubMed

Bulaqi, Haddad Arabi; Mousavi Mashhadi, Mahmoud; Safari, Hamed; Samandari, Mohammad Mahdi; Geramipanah, Farideh

2015-06-01

Implants in posterior regions of the jaw require short dental implants with long crown heights, leading to increased crown-to-implant ratios and mechanical stress. This can lead to fracture and screw loosening. The purpose of this study was to investigate the dynamic nature and behavior of prosthetic components and preimplant bone and evaluate the effect of increased crown height space (CHS) and crown-to-implant ratio on stress concentrations under external oblique forces. The severely resorbed bone of a posterior mandible site was modeled with Mimics and Catia software. A second mandibular premolar tooth was modeled with CHS values of 8.8, 11.2, 13.6, and 16 mm. A Straumann implant (4.1×8 mm), a directly attached crown, and an abutment screw were modeled with geometric data and designed by using SolidWorks software. Abaqus software was used for the dynamic simulation of screw tightening and the application of an external load to the buccal cusp at a 75.8-degree angle with the occlusal plane. The distribution of screw load and member load at each step was compared, and the stress values were calculated within the dental implant complex and surrounding bone. During tightening, the magnitude and distribution of the preload and clamp load were uniform and equal at the cross section of all CHSs. Under an external load, the screw load decreased and member load increased. An increase in the CHS caused the corresponding distribution to become more nonuniform and increased the maximum compressive and tensile stresses in the preimplant bone. Additionally, the von Mises stress decreased at the abutment screw and increased at the abutment and fixture. Under nonaxial forces, increased CHS does not influence the decrease in screw load or increase in member load. However, it contributes to screw loosening and fatigue fracture by skewing the stress distribution to the transverse section of the implant. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

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

PubMed

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

2013-05-01

All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. THE MEAN FRACTURE STRENGTHS WERE AS FOLLOWS: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (P<.001). Lava CAD/CAM zirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain.

Sinterable Ceramic Powders from Laser-Heated Gases.

DTIC Science & Technology

1988-02-01

ether . carboxylic acid. and aldehyde clases: water is also included.Acrigto William and Goodman.’ a single crystalline sili- The single-crstalline...represent commonly available organic families, Including aliphatic and aromatic hydrocarbons, chlorides, ethers , ketones , esters, alcohols, aldehydes...Hydrocarbons Ketone Amine Chlorides Low-alcohols 8f . Ether Ester - _Aldehyde Ether Ketones High-alcohols 04 Carboxylic Ester I acid Ether o . Nitrile

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

PubMed

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 (P<.001). At the facial margin, 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 (P<.001). However, the mean percentage dye penetration was significantly correlated with the vertical and horizontal marginal 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 (P<.01 in each instance). A significantly smaller vertical marginal discrepancy was found with the interim crowns fabricated by CAD/CAM as compared with PMMA crowns; however, this difference was not observed for the horizontal component. The percentage dye penetration was correlated with vertical and horizontal discrepancies at the facial surface for the Jet interim crowns and with horizontal discrepancies at the lingual surface for the Caulk interim crowns. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Tree crown conditions in Missouri, 2000-2003

Treesearch

KaDonna C. Randolph; W. Keith Moser

2009-01-01

The Forest Service, U.S. Department of Agriculture, Forest Inventory and Analysis (FIA) Program uses visual assessments of tree crown condition to monitor changes and trends in forest health. This report describes three FIA tree crown condition indicators (crown dieback, crown density, and foliage transparency) and sapling crown vigor measured in Missouri between 2000...

Descriptive statistics of tree crown condition in the Northeastern United States

Treesearch

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

2010-01-01

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

Fracture strength and fatigue resistance of all-ceramic molar crowns manufactured with CAD/CAM technology.

PubMed

Zahran, Mohammed; El-Mowafy, Omar; Tam, Laura; Watson, Philip A; Finer, Yoav

2008-07-01

All-ceramic crowns are subject to fracture during function, especially in the posterior area. The use of yttrium-stabilized zirconium-oxide ceramic as a substructure for all-ceramic crowns to improve fracture resistance is unproven. The aim of this study was to compare fracture strength and fatigue resistance of new zirconium-oxide and feldspathic all-ceramic crowns made with computer-aided design/computer-aided manufacturing (CAD/CAM). An ivorine molar was prepared to receive an all-ceramic crown. Using epoxy resin, 40 replication dies were made of the prepared tooth. Twenty feldspathic all-ceramic crowns (Vita Mark II) (VMII) and 20 zirconium-oxide crown copings (In-Ceram YZ) (YZ) were made using CAD/CAM technique (CEREC-3D). The YZ copings were sintered and veneered manually with a fine-particle ceramic (VM9). All crowns were cemented to their respective dies using resin cement (Panavia F 2.0). Ten crowns in each group were subjected to compressive fatigue loading in a universal testing machine (instron). The other ten crowns from each group were loaded to fracture at a crosshead speed of 1 mm/min. Data were statistically analyzed using independent t-test and Fisher's exact test at alpha= 0.05. There was a significant difference between the survival rates of the two materials during the fatigue test (p < 0.001). All VMII crowns survived without any crack formation, while all YZ crowns fractured (40%) or developed cracks (60%). All the YZ crown fractures occurred within the veneering layer during the fatigue test. There was no significant difference in mean fracture load between the two materials (p= 0.268). Mean fracture loads (standard deviation) in N were: 1459 (492) for YZ crowns and 1272 (109) for VMII crowns. The performance of VMII crowns was superior to YZ crowns in the fatigue test. The premature fractures and cracks of the YZ crowns were attributed to weakness in the YZ veneer layer or in the core/veneer bond.

Molecular Signatures of Methanogens in Cultures and Environmental Samples

NASA Astrophysics Data System (ADS)

Summons, R. E.; Embaye, T.; Jahnke, L. L.; Baumgartner, M.

2002-12-01

The core lipids of methanogens comprise C20 and C40 isoprenoid chains, linked through ether bonds to glycerol. Additional structural diversity is encoded into the polar head groups that are attached to the glycerol ether cores. These compounds are potentially very useful as taxonomic markers in microbial mats and other environmental samples while the nature of the hydrocarbon chains provide a means to identify methanogenic inputs to ancient sediments. The structural diversity of methanogen polar lipids is most valuable when it can be directly correlated to 16S rRNA phylogeny. On the other hand, this diversity can also leads to analytical challenges because there is no single approach that works for all structural types. While some intact methanogen lipids have been identified using mass spectrometry and NMR spectroscopy, the most common means of analysing the lipid cores involves cleavage of the ether bonds using HI and subsequent reduction of the alkyl iodides to hydrocarbons with LiAlH4. One class of methanogenic lipids, the 3?-hydroxyarchaeols, escaped detection for some years because strong acid treatments in the analysis protocols destroyed hydroxyl-containing isoprenoid chains. We have been systematically re-examining the lipids of methanogens, using milder procedures involving weak acid hydrolysis of polar head groups, derivatisation to form trimethylsilyl ethers and analysis by GC-MS. As well as archaeol, sn-2- and sn-3-hydroxyarchaeol, we have tentatively identified a dihydroxyarchaeol in several Methanococcus sp. For Methanococcus thermolithotrophicus an analysis of the total lipid extracts using BBr3 as an ether cleavage reagent followed by LiBEt3H, reduction revealed a very complex mixture consisting of phytane, phytenes, biphytane, biphytenes and a suite of related alcohols. The latter compounds were analysed by GC-MS as their trimethylsilyl ethers and found to comprise a mixture tentatively identified as phytan-N-ol and biphytan-N-ol where N= 3 or 7 or 11 or 15. Apart from phytan-3-ol, these compounds appear to have been overlooked in previous analyses of methanogen lipids. Methanopyrus kandleri, a hyperthermophile that is distinguished from other methanogens by some unusual biochemical features, is also differentiated by having biphytanyl chains with cyclopentane rings. This is a structural feature more commonly found in the Crenarchaeota. We are applying this biomarker methodology to environmental samples in studies of the spatial distribution of methanogenesis relative to other physiologies.

Alkali metal complexes of a phosphine-borane-stabilised carbanion: influence of co-ligands on structure.

PubMed

Izod, Keith; Wills, Corinne; Clegg, William; Harrington, Ross W

2007-09-07

The adducts [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n)](m) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K](infinity) (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta)](n) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta)](2) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.

Descriptive statistics of tree crown condition in California, Oregon, and Washington

Treesearch

KaDonna C. Randolph; Sally J. Campbell; Glenn Christensen

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 tree crown condition indicators (crown dieback, crown density, foliage transparency, and sapling crown vigor) measured in California, Oregon, and Washington between 1996 and 1999....

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

Treesearch

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...

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

Treesearch

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...

A Mechanistical Study on the Formation of Dimethyl Ether (CH3OCH3) and Ethanol (CH3CH2OH) in Methanol-containing Ices and Implications for the Chemistry of Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Góbi, Sándor; Abplanalp, Matthew J.; Kaiser, Ralf I.

2018-01-01

The underlying formation mechanisms of complex organic molecules (COMs)—in particular, structural isomers—in the interstellar medium (ISM) are largely elusive. Here, we report new experimental findings on the role of methanol (CH3OH) and methane (CH4) ices in the synthesis of two C2H6O isomers upon interaction with ionizing radiation: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The present study reproduces the interstellar abundance ratios of both species with ethanol to dimethyl ether branching ratios of (2.33 ± 0.14):1 suggesting that methanol and methane represents the key precursor to both isomers within interstellar ices. Exploiting isotopic labeling combined with reflectron time-of-flight mass spectrometry (Re-TOF-MS) after isomer selective vacuum ultra-violet (VUV) photoionization of the neutral molecules, we also determine the formation mechanisms of both isomers via radical–radical recombination versus carbene (CH2) insertion with the former pathway being predominant. Formation routes to higher molecular weight reaction products such as ethylene glycol (HOCH2CH2OH), dimethyl peroxide (CH3OOCH3), and methoxymethanol (CH3OCH2OH) are discussed briefly as well.

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

PubMed Central

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, possibly caused by dissolution and wear of the glaze. Statistically significant differences in surface texture (p = 0.0013) and crown wear (p = 0.0078) were found at year 3 between the metal-ceramic crowns and the lithium-disilicate-based crowns. Conclusion Based on the 11 criteria, the clinical performance of ceramic-ceramic crowns was comparable to that of the metal-ceramic crowns after 2 years; however, gradual roughening occurred between years 2 and 3, which resulted in differences in surface texture and wear. PMID:22978697

Biodegradation of bis(1-chloro-2-propyl) ether via initial ether scission and subsequent dehalogenation by Rhodococcus sp. strain DTB.

PubMed

Moreno Horn, Marcus; Garbe, Leif-Alexander; Tressl, Roland; Adrian, Lorenz; Görisch, Helmut

2003-04-01

Rhodococcus sp. strain DTB (DSM 44534) grows on bis(1-chloro-2-propyl) ether (DDE) as sole source of carbon and energy. The non-chlorinated diisopropyl ether and bis(1-hydroxy-2-propyl) ether, however, did not serve as substrates. In ether degradation experiments with dense cell suspensions, 1-chloro-2-propanol and chloroacetone were formed, which indicated that scission of the ether bond is the first step while dehalogenation of the chlorinated C(3)-compounds occurs at a later stage of the degradation pathway. Inhibition of ether scission by methimazole suggested that the first step in degradation is catalyzed by a flavin-dependent enzyme activity. The non-chlorinated compounds 1,2-propanediol, hydroxyacetone, lactate, pyruvate, 1-propanol, propanal, and propionate also supported growth, which suggested that the intermediates 1,2-propanediol and hydroxyacetone are converted to pyruvate or to propionate, which can be channeled into the citric acid cycle by a number of routes. Total release of chloride and growth-yield experiments with DDE and non-chlorinated C(3)-compounds suggested complete biodegradation of the chlorinated ether.

Three-year clinical evaluation of two ceramic crown systems: a preliminary study.

PubMed

Etman, Maged K; Woolford, M J

2010-02-01

The clinical performance and failure mechanisms of recently introduced ceramic crown systems used to restore posterior teeth have not been adequately examined. The purpose of this prospective clinical study was to evaluate and compare the clinical performance of 2 new ceramic crown systems with that of metal ceramic crowns using modified United States Public Health Services (USPHS) criteria. Ninety posterior teeth requiring crown restorations in 48 patients were randomized into 3 equal groups (n=30) for which different crown systems were used: an experimental hot-pressed glass ceramic based on a modified lithium disilicate ceramic (IPS e.max Press), an alumina-coping-based ceramic (Procera AllCeram), and a metal ceramic (Simidur S 2 veneered with IPS Classic Porcelain). The crowns were assessed over 3 years using the modified USPHS criteria. Crowns that developed visible cracks were sectioned and removed, and the surfaces were analyzed using a scanning electron microscope (SEM). The data were analyzed using the Kruskal-Wallis nonparametric statistical test, followed by the Mann-Whitney test with Bonferroni correction (alpha=.05). USPHS evaluation showed that the IPS e.max Press and metal ceramic crowns experienced fewer clinical changes than Procera AllCeram. Visible roughness, wear, and deformity were noticed in occlusal contact areas of Procera AllCeram crowns. SEM images showed well defined wear facets in both ceramic crown systems. Kruskal-Wallis tests showed a significant difference (P<.05) in Alpha scores among the 3 crown systems. Mann-Whitney tests showed significant differences among groups. IPS e.max Press crowns demonstrated clinical behavior comparable to Procera AllCeram and metal ceramic crowns, but the wear resistance of this crown type was superior to the Procera AllCeram crowns, according to modified USPHS criteria.

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

PubMed Central

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

2013-01-01

PURPOSE All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. MATERIALS AND METHODS Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. RESULTS The mean fracture strengths were as follows: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (P<.001). Lava CAD/CAM zirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. CONCLUSION The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain. PMID:23755332

Paliperidone-associated motor tics.

PubMed

Hsieh, Ming-Han; Chiu, Nan-Ying

2014-01-01

Paliperidone-associated motor tics. Case report. We report a 30-year-old man with schizophrenia who developed motor tics (eye blinking) after treatment of paliperidone up to 15 mg daily. Tic-like symptoms, from simple eye blinking to complex Tourette-like syndrome, may occur during paliperidone treatment, especially with high dose. Crown Copyright © 2014. Published by Elsevier Inc. All rights reserved.

Evaluations and modifications of semi-selective media for improved isolation of Agrobacterium tumefaciens biovar 1 from cultivated walnut

USDA-ARS?s Scientific Manuscript database

Agrobacterium tumefaciens, the causal agent of crown gall of walnut, is an aerobic, Gram negative bacterium belonging to the family Rhizobiaceae. Like many in this group, A. tumefaciens is a common inhabitant of soil and plant host tissue. Isolation from these complex environments is difficult even ...

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

PubMed

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.

Some actions of substituted choline phenyl ethers, particularly of choline 2:6-xylyl ether

PubMed Central

Edge, N. D.; Mason, D. F. J.; Wyllie, J. H.

1957-01-01

Marked nicotine-like stimulant properties are possessed by choline phenyl ether and choline o-tolyl ether, and to a decreasing extent by choline 2:6-xylyl ether and choline 2:4:6-mesityl ether. The compounds all show neuromuscular blocking properties, which are of short duration and pass from mainly decamethonium-like to mainly curare-like as more methyl groups are added to the phenyl nucleus. This series of compounds also possesses muscarinic, weak anti-adrenaline and vasodilator properties, as well as long-lasting local anaesthetic effects in the two compounds tested by intradermal injection. PMID:13460236

Trends of polybrominated diphenyl ethers and hexabromocyclododecane in eggs of Canadian Arctic seabirds reflect changing use patterns.

PubMed

Braune, Birgit M; Letcher, Robert J; Gaston, Anthony J; Mallory, Mark L

2015-10-01

Due to the substantial use and release of polybrominated diphenyl ether (PBDE) flame retardants in North America, PBDE concentrations in North American marine biota are among the highest in the world. In this study, we compared PBDE concentrations and congener patterns in eggs of five seabird species (thick-billed murres, northern fulmars, black guillemots, glaucous gulls, black-legged kittiwakes) breeding at a colony in the Canadian Arctic in 1993, 2008 and 2013. Temporal trends of PBDEs (1975-2014) and another flame retardant, hexabromocyclododecane (HBCD) (2003-2014), were also examined in eggs of two seabird species, the thick-billed murre and northern fulmar. BDE-47 generally dominated the BDE congener profiles in eggs of all five species. Glaucous gulls had the highest concentrations of both ΣPBDE and BDE-47, and northern fulmars, the lowest. ΣPBDE concentrations increased exponentially in eggs of both thick-billed murres and northern fulmars from 1975 to 2003 with doubling times of 9.1 years in the murres and 7.2 years in the fulmars. From 2003 to 2008/09, ΣPBDE decreased rapidly in the murres and fulmars to concentrations not significantly different from those recorded in 1975 and 1987 for each species. After 2008/09, ΣPBDE concentrations plateaued. BDE-47 followed a similar temporal trend to that of ΣPBDE concentrations. These concentration trends were consistent with the phase-out of the penta- and octa-BDE products from the North American market in the mid-2000s. There was an overall decline in concentrations of HBCD in murre eggs from 2003 to 2014, whereas concentrations in the fulmar eggs increased from 2003 to 2006 followed by a decline to 2014. The ratio of HBCD to BDE-47 suggests that northern fulmars showed more of a European contaminant signature, and thick-billed murres, more of a North American signature. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

Gap Fill Materials Using Cyclodextrin Derivatives in ArF Lithography

NASA Astrophysics Data System (ADS)

Takei, Satoshi; Shinjo, Tetsuya; Sakaida, Yasushi; Hashimoto, Keisuke

2007-11-01

High planarizing gap fill materials based on β-cyclodextrin in ArF photoresist under-layer materials have been developed for fast etching in CF4 gas. Gap fill materials used in the via-first dual damascene process need to have high etch rates to prevent crowning or fencing on top of the trench after etching and a small thickness bias between the dense and blanket areas to minimize issues observed during trench lithography by narrowing the process latitude. Cyclodextrin is a circular oligomer with a nanoscale porous structure that has a high number of oxygen atoms, as calculated using the Ohnishi parameter, providing high etch rates. Additionally, since gap fill materials using cyclodextrin derivatives have low viscosities and molecular weights, they are expected to exhibit excellent flow properties and minimal thermal shrinkage during baking. In this paper, we describe the composition and basic film properties of gap fill materials; planarization in the via-first dual damascene process and etch rates in CF4 gas compared with dextrin with α-glycoside bonds in polysaccharide, poly(2-hydroxypropyl methacrylate) and poly(4-hydroxystyrene). The β-cyclodextrin used in this study was obtained by esterifying the hydroxyl groups of dextrin resulting in improved wettability on via substrates and solubility in photoresist solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate. Gap fill materials using cyclodextrin derivatives showed good planarization and via filling performance without observing voids in via holes. In addition to superior via filling performance, the etch rate of gap fill materials using β-cyclodextrin derivatives was 2.8-2.9 times higher than that of an ArF photoresist, evaluated under CF4 gas conditions by reactive ion etching. These results were attributed to the combination of both nanoscale porous structures and a high density of oxygen atoms in our gap fill materials using cyclodextrin derivatives. The cyclodextrin derivatives may be applicable as a new type of sacrificial material under the photoresist in ArF lithography.

Waste-water treatment plants are implicated as an important source of flame retardants in insectivorous tree swallows (Tachicyneta bicolor).

PubMed

Fernie, Kimberly J; Letcher, Robert J

2018-03-01

Wastewater treatment plants (WWTPs) are an important source of anthropogenic chemicals, including organic flame retardants (FRs). Limited studies indicate birds can be exposed to FRs by feeding from waters receiving WWTP effluent or in fields receiving biosolids. Expanding on our earlier study, 47 legacy and 18 new FR contaminants were characterized in the eggs of insectivorous tree swallows (Tachycineta bicolor) feeding in water bodies receiving effluent from two WWTPs and compared to those from a reference site 19 km downstream of the nearest WWTP. Of the FRs measured, polybrominated diphenyl ethers (PBDEs) dominated the FR profile, specifically BDE-47, -99, -100, -153, -154, with considerably lower concentrations of hexabromocyclododecane (HBCDD), BDE-183 and BDE-209; each detected in 96-100% of the eggs overall except HBCDD (83%). FR concentrations were usually significantly greater in eggs from the secondary WWTP versus the tertiary WWTP and/or reference site. Despite low detection rates, concentrations of new FRs, specifically pentabromobenzyl acrylate (PBBA), 1,2,-bis-(2,4,6-tribromophenoxy)ethane (BTBPE), bis(2-ethylhexyl)-tetrabromophthalate (BEHTBP), tetrabromo-o-chlorotoluene (TBCT), hexabromobenzene (HBB), α- and β-1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane (DBE-DBCH), were greater than HBCDD or BDE-209. Additional evidence that WWTPs are an important source of exposure to new FR contaminants for birds utilizing associated water bodies is that only the WTTP eggs, not the reference eggs, had measureable concentrations of PBBA, TBCT, BEHTBP, HBB, α-DBE-DBCH, 2,2',4,5,5'-pentabromobiphenyl (BB-101), pentabromoethyl benzene (PBEB), 2,4,6-tribromophenyl allyl ether (TBPAE), and tetrabromo-p-xylene (pTBX). Our study suggests that WWTPs are an important source of legacy and new FR contaminants for birds consuming prey that are associated with WWTP out-flows. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Assessing crown fire potential by linking models of surface and crown fire behavior

Treesearch

Joe H. Scott; Elizabeth D. Reinhardt

2001-01-01

Fire managers are increasingly concerned about the threat of crown fires, yet only now are quantitative methods for assessing crown fire hazard being developed. Links among existing mathematical models of fire behavior are used to develop two indices of crown fire hazard-the Torching Index and Crowning Index. These indices can be used to ordinate different forest...

Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions.

PubMed

Izod, Keith; Bowman, Lyndsey J; Wills, Corinne; Clegg, William; Harrington, Ross W

2009-05-07

A straightforward Peterson olefination reaction between either [{(Me(2)PhSi)(3)C}Li(THF)] or in situ-generated [(Me(3)Si)(2){Ph(2)P(BH(3))}CLi(THF)(n)] and paraformaldehyde gives the alkenes (Me(2)PhSi)(2)C[double bond, length as m-dash]CH(2) () and (Me(3)Si){Ph(2)P(BH(3))}C[double bond, length as m-dash]CH(2) (), respectively, in good yield. Ultrasonic treatment of with lithium in THF yields the lithium complex [{(Me(2)PhSi)(2)C(CH(2))}Li(THF)(n)](2) (), which reacts in situ with one equivalent of KOBu(t) in diethyl ether to give the potassium salt [{(Me(2)PhSi)(2)C(CH(2))}K(THF)](2) (). Similarly, ultrasonic treatment of with lithium in THF yields the lithium complex [[{Ph(2)P(BH(3))}(Me(3)Si)C(CH(2))]Li(THF)(3)](2).2THF (). The bis(phosphine-borane) [(Me(3)Si){Me(2)(H(3)B)P}CH(Me(2)Si)(CH(2))](2) () may be prepared by the reaction of [Me(2)P(BH(3))CH(SiMe(3))]Li with half an equivalent of ClSiMe(2)CH(2)CH(2)SiMe(2)Cl in refluxing THF. Metalation of with two equivalents of MeLi in refluxing THF yields the lithium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}]Li(THF)(3)](2) (), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}](2)K(2)(THF)(4)](infinity) () after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex crystallises as a discrete molecular species, the potassium complexes and crystallise as sheet and chain polymers, respectively.

Our Galactic Neighbor Hosts Complex Organic Molecules

NASA Astrophysics Data System (ADS)

Hensley, Kerry

2018-03-01

For the first time, data from the Atacama Large Millimeter/submillimeter Array (ALMA) reveal the presence of methyl formate and dimethyl ether in a star-forming region outside our galaxy. This discovery has important implications for the formation and survival of complex organic compounds importantfor the formation of life in low-metallicity galaxies bothyoung and old.No Simple Picture of Complex Molecule FormationALMA, pictured here with the Magellanic Clouds above, has observed organic molecules in our Milky Way Galaxy and beyond. [ESO/C. Malin]Complex organic molecules (those with at least six atoms, one or more of which must be carbon) are the precursors to the building blocks of life. Knowing how and where complex organic molecules can form is a key part of understanding how life came to be on Earth and how it might arise elsewhere in the universe. From exoplanet atmospheres to interstellar space, complex organic molecules are ubiquitous in the Milky Way.In our galaxy, complex organic molecules are often found in the intense environments of hot cores clumps of dense molecular gas surrounding the sites of star formation. However, its not yet fully understood how the complex organic molecules found in hot cores come to be. One possibility is that the compounds condense onto cold dust grains long before the young stars begin heating their natal shrouds. Alternatively, they might assemble themselves from the hot, dense gas surrounding the blazing protostars.Composite infrared and optical image of the N 113 star-forming region in the LMC. The ALMA coverage is indicated by the gray line. Click to enlarge. [Sewio et al. 2018]Detecting Complexity, a Galaxy AwayUsing ALMA, a team of researchers led by Marta Sewio (NASA Goddard Space Flight Center) recently detected two complex organic molecules methyl formate and dimethyl ether for the first time in our neighboring galaxy, the Large Magellanic Cloud (LMC). Previous searches for organic molecules in the LMC detected small amounts of methanol, the parentmolecule of the two newly-discovered compounds. By revealing the spectral signatures of dimethyl ether and methyl formate, Sewio and collaboratorsfurther prove thatorganic chemistry is hard at work in hot cores in the LMC.This discovery is momentous because dwarf galaxies like theLMC tend to have a lower abundance of the heavy elements that make up complex organic molecules most importantly, oxygen, carbon, and nitrogen. Beyond lacking the raw materials necessary to create complex molecules, the gas of low-metallicity galaxies does a poorer job preventing the penetration of high-energy photons. The impinging photons warm dust grains, resulting in a lower probability of forming and maintaining complex organic molecules. Despite this, organic molecules appear to beable todevelop and persist which has exciting implications for organic chemistry in low-metallicity environments.ALMA observation of emission by methyl formate in a hot core in the LMC.[Adapted from Sewio et al. 2018]A Lens into the PastIn the early universe, before the budding galaxies have had time to upcycle their abundant hydrogen into heavier elements, organic chemistry is thought to proceed slowly or not at all. The discovery of complex organic molecules in a nearby low-metallicity galaxy upends this theory and propels us toward a better understanding of the organic chemistry in the early universe.CitationMarta Sewio et al 2018ApJL853L19. doi:10.3847/2041-8213/aaa079

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

Actinide extraction methods

DOEpatents

Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

2010-09-21

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

PubMed Central

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-01-01

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. PMID:26248980

Synthesis, anticancer activity, and iron affinity of the Actinoplanes metabolite 7,8-dihydroxy-1-methylnaphtho[2,3-c]furan-4,9-dione.

PubMed

Breyer, Sandra; Effenberger-Neidnicht, Katharina; Knauer, Sebastian; Schobert, Rainer

2011-02-01

The first synthesis of 7,8-dihydroxy-1-methylnaphtho[2,3-c]furan-4,9-dione (1), an isofuranonaphthoquinone produced by an Actinoplanes strain is described. Lactone ring opening of 6-methylfuro[3,4-c]furan-1(3H)-one (4) with ortho-lithiated veratrole (3), oxidation of product alcohol 5, and Friedel-Crafts acylation of the resulting aroylcarboxylic acid 7 afforded the mono methyl ether 2 of the target compound. The latter was obtained by demethylation of 2 with BBr(3) in 14% overall yield. While mono ether 2 was distinctly more cytotoxic than catechol 1 against a panel of five cancer cell lines, only the latter showed a siderophore-like binding affinity for Fe(III) with a complex dissociation constant K(D) of approximately 10(-29) M(3) (pM = 25.9). Copyright © 2010 Elsevier Ltd. All rights reserved.

Removal of failed crown and bridge

PubMed Central

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

2012-01-01

Crown and bridge have life span of many years but they fail for a number of reasons. Over the years, many devices have been designed to remove crowns and bridges from abutment teeth. While the removal of temporary crowns and bridges is usually very straightforward, the removal of a definitive cast crown with unknown cement is more challenging. Removal is often by destructive means. There are a number of circumstances, however, in which conservative disassembly would aid the practitioner in completing restorative/endodontic procedures. There are different mechanisms available to remove a failed crown or bridge. But there is no information published about the classification of available systems for crown and bridge removal. So it is logical to classify these systems into different groups which can help a clinician in choosing a particular type of system depending upon the clinical situation. The aim of this article is to provide a classification for various crown and bridge removal systems; describe how a number of systems work; and when and why they might be used. A PubMed search of English literature was conducted up to January 2010 using the terms: Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. Additionally, the bibliographies of 3 previous reviews, their cross references as well as articles published in various journals like International Endodontic Journal, Journal of Endodontics and were manually searched. Key words:Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. PMID:24558549

Zirconia-implant-supported all-ceramic crowns withstand long-term load: a pilot investigation.

PubMed

Kohal, Ralf-J; Klaus, Gerold; Strub, Jörg R

2006-10-01

The purpose of this pilot investigation was to test whether zirconia implants restored with different all-ceramic crowns would fulfill the biomechanical requirements for clinical use. Therefore, all-ceramic Empress-1 and Procera crowns were cemented on zirconia implants and exposed to the artificial mouth. Afterwards, the fracture strength of the all-ceramic implant-crown systems was evaluated. Conventional titanium implants restored with porcelain-fused-to-metal (PFM) crowns served as controls. Sixteen titanium implants with 16 PFM crowns and 32 zirconia implants with 16 Empress-1 crowns and 16 Procera crowns each--i.e., three implant-crown groups--were used in this investigation. The titanium implants were fabricated using the ReImplant system and the zirconia implants using the Celay system. The upper left central incisor served as a model for the fabrication of the implants and the crowns. Eight samples of each group were submitted to a long-term load test in the artificial mouth (1.2 million chewing cycles). Subsequently, a fracture strength test was performed with seven of the eight crowns. The remaining eight samples of each group were not submitted to the long-term load in the artificial mouth but were fracture-tested immediately. One loaded and one unloaded sample of each group were evaluated regarding the marginal fit of the crowns. All test samples survived the exposure to the artificial mouth. Three Empress-1 crowns showed cracks in the area of the loading steatite ball. The values for the fracture load in the titanium implant-PFM crown group without artificial loading ranged between 420 and 610 N (mean: 531.4 N), between 460 and 570 N (mean: 512.9 N) in the Empress-1 crown group, and in the Procera crown group the values were between 475 and 700 N (mean: 575.7 N) when not loaded artificially. The results when the specimens were loaded artificially with 1.2 million cycles were as follows: the titanium implant-PFM crowns fractured between 440 and 950 N (mean: 668.6 N), the Empress-1 crowns between 290 and 550 N (mean: 410.7 N), and the Procera crowns between 450 and 725 N (mean: 555.5 N). No statistically significant differences could be found among the groups without artificial load. The fracture values for the PFM and the Procera crowns after artificial loading were statistically significantly higher than that for the loaded Empress-1 crowns. There was no significant difference between the PFM crown group and the Procera group. Within the limits of this pilot investigation, it seems that zirconia implants restored with the Procera crowns possibly fulfill the biomechanical requirements for anterior teeth. However, further investigations with larger sample sizes have to confirm these preliminary results. As three Empress-1 crowns showed crack development in the loading area of the steatite balls in the artificial mouth, their clinical use on zirconia implants has to be questioned.

Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure.

PubMed

Zhu, Yan; Cammers-Goodwin, Arthur; Zhao, Bin; Dozier, Alan; Dickey, Elizabeth C

2004-05-17

This study aimed to elucidate the structural nature of the polydisperse, nanoscopic components in the solution and the solid states of partially reduced polyoxomolybdate derived from the [Mo132] keplerate, [(Mo)Mo5]12-[Mo2 acetate]30. Designer tripodal hexamine-tris-crown ethers and nanoscopic molybdate coprecipitated from aqueous solution. These microcrystalline solids distributed particle radii between 2-30 nm as assayed by transmission electron microscopy (TEM). The solid materials and their particle size distributions were snap shots of the solution phase. The mother liquor of the preparation of the [Mo132] keplerate after three days revealed large species (r=20-30 nm) in the coprecipitate, whereas [Mo132] keplerate redissolved in water revealed small species (3-7 nm) in the coprecipitate. Nanoparticles of coprecipitate were more stable than solids derived solely from partially reduced molybdate. The TEM features of all material analyzed lacked facets on the nanometer length scale; however, the structures diffracted electrons and appeared to be defect-free as evidenced by Moiré patterns in the TEM images. Moiré patterns and size-invariant optical densities of the features in the micrographs suggested that the molybdate nanoparticles were vesicular.

Novel brominated flame retardants and dechloranes in three fish species from the St. Lawrence River, Canada.

PubMed

Houde, Magali; Berryman, David; de Lafontaine, Yves; Verreault, Jonathan

2014-05-01

Restrictions in the utilization of polybrominated diphenyl ether (PBDE) mixtures have led to the increased usage of alternative flame retardant additives in a wide range of commercial applications. The present study examined the occurrence of established and emerging flame retardants (FRs) in fish from a densely-populated urbanized sector of the St. Lawrence River (Montreal, Quebec, Canada). Thirty-eight PBDE congeners and sixteen emerging FRs were determined in fish belonging to three predatory species (yellow perch, northern pike, and muskellunge). The ∑PBDE in fish were up to 24,115 ng/g lipid weight (l.w.) in the apex predator muskellunge. Twelve emerging FRs including bis(2-ethylhexyl)-tetrabromophthalate (BEHTBP), pentabromoethylbenzene (PBEB), Dechlorane Plus (anti and syn), dechloranes (Dec) 602, Dec 604, Dec 604 Compound B (Dec 604 CB), and Chlordene Plus (CP) were detected (>0.01 ng/gl.w.) in the liver of muskellunge and northern pike but not in yellow perch homogenates. This is the first report of Dec 604 CB in any fish species. The bioavailability of these FRs in human-impacted aquatic ecosystems warrants further environmental assessment and toxicity testing. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Stereocontrolled Cyanohydrin Ether Synthesis through Chiral Brønsted Acid-Mediated Vinyl Ether Hydrocyanation

PubMed Central

Lu, Chunliang; Su, Xiaoge; Floreancig, Paul E.

2013-01-01

Vinyl ethers can be protonated to generate oxocarbenium ions that react with Me3SiCN to form cyanohydrin alkyl ethers. Reactions that form racemic products proceed efficiently upon converting the vinyl ether to an α-chloro ether prior to cyanide addition in a pathway that proceeds through Brønsted acid-mediated chloride ionization. Enantiomerically enriched products can be accessed by directly protonating the vinyl ether with a chiral Brønsted acid to form a chiral ion pair. Me3SiCN acts as the nucleophile and PhOH serves as a stoichiometric proton source in a rare example of an asymmetric bimolecular nucleophilic addition reaction into an oxocarbenium ion. Computational studies provide a model for the interaction between the catalyst and the oxocarbenium ion. PMID:23968162

[Clinical evaluation of the effect of gold alloy and Ni-Cr alloy porcelain fused metal crown restorations].

PubMed

Sun, Wei-ge; Liu, Xiang-hui; Zhang, Ling; Zhang, Chun; Xie, Ming-yi; Zhou, Wen-juan

2009-02-01

To observe the clinical effect of gold alloy porcelain fused metal (PFM) crown restoration and Ni-Cr alloy PFM crown restoration. A total of 168 teeth from 48 patients were restored with gold alloy PFM crown. The other 48 patients, with a total of 179 teeth were restored with Ni-Cr alloy PFM crown. They were examined in integrality, retention, shade, cervical margin, and gingival health immediately, 6 months, one year, two years ,and three years after restoration. The date was analyzed by rank sum test using SPSS12.0 software package. The clinical effect of Ni-Cr alloy PFM crown was as good as gold alloy PFM crown when checked up after cementation at once. However, when they were examined 6 months, one year, two years ,and three years after restoration, the clinical effect of gold alloy PFM crown group was significantly better than that of Ni-Cr alloy PFM crown, P<0.05. The gold alloy PFM crown has better properties than Ni-Cr alloy PFM crown as a kind of long-term restoration, especially on the aspect of shade.

Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

F Calaza; T Chen; D Mullins

2011-12-31

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tiltmore » away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.« less

Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R

2011-01-01

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tiltmore » away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.« less

Effect of p-amino-diphenyl ethers on hepatic microsomal cytochrome P450.

PubMed

Jiang, Huidi; Xuan, Guida

2003-09-01

The present paper aims to investigate whether p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450. Mice were given daily intraperitoneal (ip) injections of p-amino-2',4'-dichlorodiphenyl ether (0.25 mmol/kg) or p-amino-4'-methyldiphenyl ether (0.25 mmol/kg) for 4 days and tested at 24 h and 48 h after the last dose injection. The results showed the mice pentobarbital sleeping time was shorter and the P450 content of hepatic microsome increased significantly in the group pretreated with p-amino-4'-methyldiphenyl ether when compared with the control group, while in mice pretreated with p-amino-2',4'-dichlorodiphenyl ether the hepatic microsome P450 content increased but the pentobarbital sleeping time was extended in clear contrast to the control group. The sleeping time of the phenobarbital group (80 mg/kg daily ip injection for 4 days) was shortened at 24 h after the last injection with increased P450 content of hepatic microsome, but it showed no difference at 48 h. The zoxazolamine-paralysis times of mice treated with p-amino-2',4'-dichlorodiphenyl ether were longer than those of the control mice, while the same dose of zoxazolamine did not lead to paralysis in mice pretreated with BNF. p-Amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether inhibited the activity of 7-ethoxyresorufin O-deethylase from rat hepatic microsome induced by BNF in vitro by 70.0% and 50.1% respectively. These results suggest that p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450.

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

Treesearch

Chris Toney; Matthew C. Reeves

2009-01-01

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

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

Treesearch

Leon S. Minckler; Samuel F. Gingrich

1970-01-01

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

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

Treesearch

Russell A. Parsons; William Mell; Peter McCauley

2010-01-01

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

URANIUM PURIFICATION PROCESS

DOEpatents

Winters, C.E.

1957-11-12

A method for the preparation of a diethyl ether solution of uranyl nitrate is described. Previously the preparation of such ether solutions has been difficult and expensive, since crystalline uranyl nitrate hexahydrate dissolves very slowly in ether. An improved method for effecting such dissolution has been found, and it comprises adding molten uranyl nitrate hexahydrate at a temperature of 65 to 105 deg C to the ether while maintaining the temperature of the ether solvent below its boiling point.

Comparative evaluation of marginal leakage of provisional crowns cemented with different temporary luting cements: In vitro study.

PubMed

Arora, Sheen Juneja; Arora, Aman; Upadhyaya, Viram; Jain, Shilpi

2016-01-01

As, the longevity of provisional restorations is related to, a perfect adaptation and a strong, long-term union between restoration and teeth structures, therefore, evaluation of marginal leakage of provisional restorative materials luted with cements using the standardized procedures is essential. To compare the marginal leakage of the provisional crowns fabricated from Autopolymerizing acrylic resin crowns and bisphenol A-glycidyl dimethacrylate (BIS-GMA) resin crowns. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin crowns and BIS-GMA resin crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin (SC-10) crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from BIS-GMA resin crowns (Protemp 4) cemented with different temporary luting cements. Freshly extracted 60 maxillary premolars of approximately similar dimensions were mounted in dental plaster. Tooth reduction with shoulder margin was planned to use a customized handpiece-holding jig. Provisional crowns were prepared using the wax pattern fabricated from computer aided designing/computer aided manufacturing milling machine following the tooth preparation. Sixty provisional crowns were made, thirty each of SC-10 and Protemp 4 and were then cemented with three different luting cements. Specimens were thermocycled, submerged in a 2% methylene blue solution, then sectioned and observed under a stereomicroscope for the evaluation of marginal microleakage. A five-level scale was used to score dye penetration in the tooth/cement interface and the results of this study was analyzed using the Chi-square test, Mann-Whitney U-test, Kruskal-Wallis H-test and the results were statistically significant P < 0.05 the power of study - 80%. Marginal leakage was significant in both provisional crowns cemented with three different luting cements along the axial walls of teeth (P < 0.05) confidence interval - 95%. The temporary cements with eugenol showed more microleakage than those without eugenol. SC-10 crowns showed more microleakage compared to Protemp 4 crowns. SC-10 crowns cemented with Kalzinol showed maximum microleakage and Protemp 4 crowns cemented with HY bond showed least microleakage.

Zinc(II) complexes with heterocyclic ether, acid and amide. Crystal structure, spectral, thermal and antibacterial activity studies

NASA Astrophysics Data System (ADS)

Jabłońska-Wawrzycka, Agnieszka; Rogala, Patrycja; Czerwonka, Grzegorz; Hodorowicz, Maciej; Stadnicka, Katarzyna

2016-02-01

The reaction of zinc salts with heterocyclic ether (1-ethoxymethyl-2-methylimidazole (1-ExMe-2-MeIm)), acid (pyridine-2,3-dicarboxylic acid (2,3-pydcH2)) and amide (3,5-dimethylpyrazole-1-carboxamide (3,5-DMePzCONH2)) yielded three new zinc complexes formulated as [Zn(1-ExMe-2-MeIm)2Cl2] 1, fac-[Zn(H2O)6][Zn(2,3-pydcH)3]22 and [Zn(3,5-DMePz)2(NCO)2] 3. Complexes of 1 and 3 are four-coordinated with a tetrahedron as coordination polyhedron. However, compound 2 forms an octahedral cation-anion complex. The complex 3 was prepared by eliminating of the carboxamide group from the ligand and then the 3,5-dimethylpyrazole (3,5-DMePz) and isocyanates formed were employed as new ligands. The IR and X-ray studies have confirmed a bidentate fashion of coordination of the 2,3-pydcH and monodentate fashion of coordination of the 1-ExMe-2-MeIm and 3,5-DMePz to the Zn(II) ions. The crystal packing of Zn(II) complexes are stabilized by intermolecular classical hydrogen bonds of O-H⋯O and N-H⋯O types. The most interesting feature of the supramolecular architecture of complexes is the existence of C-H⋯O, C-H⋯Cl and C-H⋯π interactions and π⋯π stacking, which also contributes to structural stabilisation. The correlation between crystal structure and thermal stability of zinc complexes is observed. In all compounds the fragments of ligands donor-atom containing go in the last steps. Additionally, antimicrobial activities of compounds were carried out against certain Gram-positive and Gram-negative bacteria and counts of CFU (colony forming units) were also determined. The achieved results confirmed a significant antibacterial activity of some tested zinc complexes. On the basis of the Δ log CFU values the antibacterial activity of zinc complexes follows the order: 3 > 2 > 1. Influence a number of N-donor atoms in zinc environment on antibacterial activity is also observed.

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

PubMed

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) (P<.05). Both fabrication systems and finish line configurations significantly influenced the absolute marginal discrepancy (P<.05). The lithium disilicate glass ceramic crown (IPS e.max®press) had significantly smaller marginal 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.

In-vitro performance and fracture strength of thin monolithic zirconia crowns

PubMed Central

Weigl, Paul; Wu, Yanyun; Felber, Roland; Lauer, Hans-Christoph

2018-01-01

PURPOSE All-ceramic restorations required extensive tooth preparation. The purpose of this in vitro study was to investigate a minimally invasive preparation and thickness of monolithic zirconia crowns, which would provide sufficient mechanical endurance and strength. MATERIALS AND METHODS Crowns with thickness of 0.2 mm (group 0.2, n=32) or of 0.5 mm (group 0.5, n=32) were milled from zirconia and fixed with resin-based adhesives (groups 0.2A, 0.5A) or zinc phosphate cements (groups 0.2C, 0.5C). Half of the samples in each subgroup (n=8) underwent thermal cycling and mechanical loading (TCML)(TC: 5℃ and 55℃, 2×3,000 cycles, 2 min/cycle; ML: 50 N, 1.2×106 cycles), while the other samples were stored in water (37℃/24 h). Survival rates were compared (Kaplan-Maier). The specimens surviving TCML were loaded to fracture and the maximal fracture force was determined (ANOVA; Bonferroni; α=.05). The fracture mode was analyzed. RESULTS In both 0.5 groups, all crowns survived TCML, and the comparison of fracture strength among crowns with and without TCML showed no significant difference (P=.628). Four crowns in group 0.2A and all of the crowns in group 0.2C failed during TCML. The fracture strength after 24 hours of the cemented 0.2 mm-thick crowns was significantly lower than that of adhesive bonded crowns. All cemented crowns provided fracture in the crown, while about 80% of the adhesively bonded crowns fractured through crown and die. CONCLUSION 0.5 mm thick monolithic crowns possessed sufficient strength to endure physiologic performance, regardless of the type of cementation. Fracture strength of the 0.2 mm cemented crowns was too low for clinical application. PMID:29713427

Amended final report on the safety assessment of PPG-40 butyl ether with an addendum to include PPG-2, -4, -5, -9, -12, -14, -15, -16, -17, -18, -20, -22, -24, -26, -30, -33, -52, and -53 butyl ethers.

PubMed

Lanigan, R S

2001-01-01

The Polypropylene Glycol (PPG) Butyl Ethers function as skinand hair-conditioning agents in cosmetics. Intestinal absorption of the PPG Butyl Ethers was inversely proportional to the molecular weight. In general, the toxicity of the PPG Butyl Ethers decreased as the molecular weight increased. In acute studies, moderate intraperitoneal (IP) doses of various PPG Butyl Ethers caused convulsive seizures in mice and anesthetized dogs, and large oral doses caused decreased activity, anuria, renal tubular swelling and necrosis, and hepatic swelling and necrosis. PPG-2 Butyl Ether vapors were nontoxic by the inhalation route. PPG-2 Butyl Ether was nontoxic in short-term feeding and dermal exposure studies in rats. In animal irritation studies, PPG-2 Butyl Ether caused minor, transient erythema and desquamation; in addition, erythema, edema, ecchymosis, necrosis, and other changes were observed during an acute percutaneous study. PPG-2 Butyl Ether also caused minor to moderate conjunctival irritation and minor corneal injury. PPG-2 Butyl Ether when dermally applied was nontoxic to pregnant rats and was nonteratogenic at doses up to 1.0 ml/kg/day. PPG BE800 at concentrations of 0.001% to 0.26% in feed was noncarcinogenic to rats after 2 years of treatment. In clinical studies, PPG BE800 was nonirritating and nonsensitizing to the skin when tested using 200 subjects. PPG-40 Butyl Ether was neither an irritant nor a sensitizer in a repeat-insult patch test using 112 subjects. Although clinical testing did not indicate significant skin irritation is produced by these ingredients, the animal test data did indicate the potential that these ingredients can be irritating. Therefore, it was concluded that the PPG Butyl Ethers can be used safely in cosmetic products if they are formulated to avoid irritation. Data on the component ingredients, Propylene Glycol, PPG, and n-Butyl Alcohol, from previous cosmetic ingredient safety assessments were also considered and found to support the safety of PPG Butyl Ethers.

Coordination of crown structure, leaf plasticity and carbon gain within the crowns of three winter-deciduous mature trees.

PubMed

Uemura, Akira; Harayama, Hisanori; Koike, Nobuya; Ishida, Atsushi

2006-05-01

We examined the vertical profiles of leaf characteristics within the crowns of two late-successional (Fagus crenata Blume and Fagus japonica Maxim.) and one early-successional tree species (Betula grossa Sieb. et Zucc.) in a Japanese forest. We also assessed the contributions of the leaves in each crown layer to whole-crown instantaneous carbon gain at midday. Carbon gain was estimated from the relationship between electron transport and photosynthetic rates. We hypothesized that more irradiance can penetrate into the middle of the crown if the upper crown layers have steep leaf inclination angles. We found that such a crown has a high whole-crown carbon gain, even if leaf traits do not change greatly with decreasing crown height. Leaf area indices (LAIs) of the two Fagus trees (5.26-5.52) were higher than the LAI of the B. grossa tree (4.50) and the leaves of the F. crenata tree were more concentrated in the top crown layers than were leaves of the other trees. Whole-crown carbon gain per unit ground area (micromol m(-2) ground s(-1)) at midday on fine days in summer was 16.3 for F. crenata, 11.0 for F. japonica, and 20.4 for B. grossa. In all study trees, leaf dry mass (LMA) and leaf nitrogen content (N) per unit area decreased with decreasing height in the crown, but leaf N per unit mass increased. Variations (plasticity) between the uppermost and lowermost crown layers in LMA, leaf N, the ratio of chlorophyll to N and the ratio of chlorophyll a to b were smaller for F. japonica and B. grossa than for F. crenata. The light extinction coefficients in the crowns were lower for the F. japonica and B. grossa trees than for the F. crenata tree. The leaf carbon isotope ratio (delta(13)C) was higher for F. japonica and B. grossa than for F. crenata, especially in the mid-crown. These results suggest that, in crowns with low leaf plasticity but steep leaf inclination angles, such as those of F. japonica and B. grossa trees, irradiance can penetrate into the middle of the crowns, thereby enhancing whole-crown carbon gain.

Comparison of clinical results for the use of ethyl acetate and diethyl ether in the formalin-ether sedimentation technique performed on polyvinyl alcohol-preserved specimens.

PubMed Central

Garcia, L S; Shimizu, R

1981-01-01

One hundred fecal specimens preserved in polyvinyl alcohol fixative were examined by the Formalin-ether sedimentation technique with ethyl acetate substituted for diethyl ether. Technical performance of the procedures, appearance and amount of sediment obtained, and organism morphology were comparable. Also, ethyl acetate is less flammable and, therefore, less dangerous to use than diethyl ether. Results of parasite recovery when diethyl ether or ethyl acetate was used revealed few clinical relevant differences, most of which could also have been attributed to other variables inherent in this type of diagnostic testing. PMID:7229014

Propenyl ether monomers for photopolymerization

DOEpatents

Crivello, J.V.

1996-10-22

Propenyl ether monomers of formula A(OCH{double_bond}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 the above formula 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.

Propenyl ether monomers for photopolymerization

DOEpatents

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.

Process for making propenyl ethers and photopolymerizable compositions containing them

DOEpatents

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.

Mechanisms of selective cleavage of C–O bonds in di-aryl ethers in aqueous phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiayue; Zhao, Chen; Mei, Donghai

2014-01-01

A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH 3-, and OH- diphenyl ethers has been explored over Ni/SiO 2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H 2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H 2 pressure. In contrast tomore » diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC 6H 4O* (adsorbed), which is then cleaved to phenol (C 6H 5O* with added H*) and H 2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC 6H 4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO 2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h -1) > diphenyl ether (26 h -1) > di-p-tolyl ether (1.3 h -1), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol -1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol -1) to di-p-tolyl ether (105 kJ∙mol -1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.« less

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

PubMed

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.