60 resultados para Wicquefort, Abraham van, 1606-1682.
Resumo:
Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethyl-sulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by H-1 NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined.
Resumo:
Imidazo[4,5-f]-1,10-phenanthroline and pyrazino[2,3-f]-1,10-phenanthroline substituted with long alkyl chains are versatile ligands for the design of metallomesogens because of the ease of ligand substitution. Whereas the ligands and the corresponding rhenium(I) complexes were not liquid-crystalline, mesomorphism was observed for the corresponding ionic ruthenium(II) complexes with chloride, hexafluorophosphate, and bistriflimide counterions. The mesophases were identified as smectic A phases by high-temperature small-angle X-ray scattering (SAXS) using synchrotron radiation. The transition temperatures depend on the anion, the highest temperatures being observed for the chloride salts and the lowest for the bistriflimide salts. The ruthenium(II) complexes are examples of luminescent ionic liquid crystals.
Resumo:
Highly luminescent anionic samarium(III) beta-diketonate and dipicolinate complexes were dissolved in the imidazolium ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. The solubility of the complexes in the ionic liquid was ensured by a careful choice of the countercation of the samarium(III) complex. The samarium(III) complexes that were considered are [C(6)mim][SM(tta)(4)], where tta is 2-thenoyltrifluoroacetonate; [C(6)mim][Sm(nta)(4)], where nta is 2-naphthoyltrifluoroacetonate; [C(6)mim][Sm(hfa)(4)], where hfa is hexafluoroacetylacetonate; and [choline](3)-[Sm(dpa)(3)], where dpa is pyridine-2,6-dicarboxylate (dipicolinate) and [choline](+) is (2-hydroxyethyl)trimethyl ammonium. The crystal structures of the tetrakis samarium(III) P-diketonate complexes revealed a distorted square antiprismatic coordination for the samarium(III) ion in all three cases. Luminescence spectra were recorded for the samarium(III) complexes dissolved in the imidazolium ionic liquid as well as in a conventional solvent, that is, acetonitrile or water for the beta-diketonate and dipicolinate complexes, respectively. These experiments demonstrate that [C(6)mim][Tf2N] is a suitable spectroscopic solvent for studying samarium(III) luminescence. High-luminescence quantum yields were observed for the samarium(III) beta-diketonate complexes in solution.
Coordination environment of [UO2Br4](2-) in ionic liquids and crystal structure of [Bmim](2)[UO2Br4]
Resumo:
The complex formed by the reaction of the uranyl ion, UO22+, with bromide ions in the ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmiml[Tf2N]) and methyl-tributylammonium bis(trifluoromethylsulfonyl)imide ([MeBu3N][Tf2N]) has been investigated by UV-Vis and U L-III-edge EXAFS spectroscopy and compared to the crystal structure of [Bmim](2)[UO2Br4]. The solid state reveals a classical tetragonal bipyramid geometry for [UO2Br4](2-) with hydrogen bonds between the Bmim(+) and the coordinated bromides. The UV-Vis spectroscopy reveals the quantitative formation of [UO2Br4](2-) when a stoichiometric amount of bromide ions is added to UO2(CF3SO3)(2) in both Tf2N-based ionic liquids. The absorption spectrum also suggests a D-4h symmetry for [UO2Br4](2-) in ionic liquids, as previously observed for the [UO2Cl4](2-) congener. EXAFS analysis supports this conclusion and demonstrates that the [UO2Br4](2-) coordination polyhedron is maintained in the ionic liquids without any coordinating solvent or water molecules. The mean U-O and U-Br distances in the solutions, determined by EXAFS, are, respectively, 1.766(2) and 2.821(2)angstrom in [Bmim][Tf2N], and, respectively, 1.768(2) and 2.827(2) angstrom, in [MeBu3N][Tf2N]. Similar results are obtained in both ionic liquids indicating no significant influence of the ionic liquid cation either on the complexation reaction or on the structure of the uranyl species. (C) 2009 Elsevier Ltd. All rights reserved.
Resumo:
We present comprehensive photometric and spectroscopic observations of the faint transient SN 2008S discovered in the nearby galaxy NGC 6946. SN 2008S exhibited slow photometric evolution and almost no spectral variability during the first nine months, implying a long photon diffusion time and a high-density circumstellar medium. Its bolometric luminosity (similar or equal to 10(41) erg s(-1) at peak) is low with respect to most core-collapse supernovae but is comparable to the faintest Type II-P events. Our quasi-bolometric light curve extends to 300 d and shows a tail phase decay rate consistent with that of Co-56. We propose that this is evidence for an explosion and formation of Ni-56 (0.0014 +/- 0.0003 M-circle dot). Spectra of SN 2008S show intense emission lines of H alpha, [Ca II] doublet and Ca II near-infrared (NIR) triplet, all without obvious P-Cygni absorption troughs. The large mid-infrared (MIR) flux detected shortly after explosion can be explained by a light echo from pre-existing dust. The late NIR flux excess is plausibly due to a combination of warm newly formed ejecta dust together with shock-heated dust in the circumstellar environment. We reassess the progenitor object detected previously in Spitzer archive images, supplementing this discussion with a model of the MIR spectral energy distribution. This supports the idea of a dusty, optically thick shell around SN 2008S with an inner radius of nearly 90 AU and outer radius of 450 AU, and an inferred heating source of 3000 K. The luminosity of the central star is L similar or equal to 10(4.6) L-circle dot. All the nearby progenitor dust was likely evaporated in the explosion leaving only the much older dust lying further out in the circumstellar environment. The combination of our long-term multiwavelength monitoring data and the evidence from the progenitor analysis leads us to support the scenario of a weak electron-capture supernova explosion in a super-asymptotic giant branch progenitor star (of initial mass 6-8 M-circle dot) embedded within a thick circumstellar gaseous envelope. We suggest that all of main properties of the electron-capture SN phenomenon are observed in SN 2008S and future observations may allow a definitive answer.
Resumo:
The near-infrared luminescence properties of three (E)-N-hexadecyl-N',N'-dimethylamino-stilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato) lanthanide(III) complexes are described. These three complexes, containing trivalent neodymium, erbium and ytterbium, respectively, show near-infrared luminescence in acetonitrile solution upon UV irradiation. Luminescence decay times have been measured. The complexes consist of a positively charged hemicyanine chromophore with a long alkyl chain and a tetrakis(pyrazolonato) lanthanide(III) anion. Because of the absence of an alpha-hydrogen atom in the pyrazolonato ligands, and because of the saturation of the coordination sphere by four bidentate ligands, the luminescence properties are enhanced when compared to, e.g. quinolinate complexes. (C) 2007 Elsevier Ltd. All rights reserved.
Resumo:
Choline saccharinate and choline acesulfamate are two examples of hydrophilic ionic liquids, which can be prepared from easily available starting materials (choline chloride and a non-nutritive sweetener). The (eco)toxicity of these ionic liquids in aqueous solution is very low in comparison to other types of ionic liquids. A general method for the synthesis and purification of hydrophilic ionic liquids is presented. The method consists of a silver-free metathesis reaction, followed by purification of the ionic liquid by ion-exchange chromatography. The crystal structures show a marked difference in hydrogen bonding between the two ionic liquids, although the saccharinate and the acesulfamate anions show structural similarities. The optimized structures, the energetics, and the charge distribution of cation-anion pairs in the ionic liquids were studied by density functional theory (DFT) and second-order (Moller-Plesset) perturbation theory calculations. The occupation of the non-Lewis orbitals was considered to obtain a qualitative picture of the Lewis structures. The calculated interaction energies and the dipole moments for the ion pairs in the gas phase were discussed.
Resumo:
Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.
Resumo:
The solubility and uniform distribution of lanthanide complexes in sol-get glasses can be improved by covalently linking the complexes to the sol-gel matrix. In this study, several lanthanide beta-diketonate complexes (Ln = Nd, Sm, Eu, Tb, Er, Yb) were immobilized on a 1,10-phenanthroline functionalized sol-gel glass. For the europium(Ill) complex, a sol-gel material of diethoxydimethylsilane (DEDMS) with polymer-like properties was derived. For the other lanthanide complexes, the sol-gel glass was prepared by using a matrix of tetramethoxysilane (TMOS) and DEDMS. Both systems were prepared under neutral reaction conditions. High-resolution emission and excitation spectra were recorded. The luminescence lifetimes were measured. (c) 2004 Elsevier B.V. All rights reserved.
Resumo:
A new type of near-infrared emitting rare-earth complex has been synthesised, consisting of three bis(perfluoroalkylsulfonyl)imide ligands and one 1,10-phenanthroline molecule. The chelate rings formed by the rare-earth ion and the bidentate ligands do not contain any carbon atoms and can hence be considered as 'inorganic' chelate rings. The absence of C-H stretching vibration modes in the first coordination sphere of the rare-earth ion and the presence of a light-harvesting moiety (1,10-phenanthroline) bound to the rare-earth ion result in a complex that can be efficiently excited and exhibits intense near-infrared luminescence. (C) 2004 Elsevier B.V. All rights reserved.
Resumo:
Uranium(VI) oxide has been dissolved in three different ionic liquids functionalized with a carboxyl group: betainium bis[trifluoromethyl)sulfonyl]imide, 1-(carboxymethyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and N-(carboxymethyl)-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide. The dissolution process results in the formation of uranyl complexes with zwitterionic carboxylate ligands and bis[trifluoromethyl)sulfonyl]imide (bistriflimide) counterions. An X-ray diffraction study on single crystals of the uranyl complexes revealed that the crystal structure strongly depends on the cationic core appended to the carboxylate groups. The betainium ionic liquid gives a dimeric uranyl complex, the imidazolium ionic liquid a monomeric complex, and the pyrrolidinium ionic liquid a one-dimensional polymeric uranyl complex, Extended X-ray absorption fine structure measurements have been performed on the betainium uranyl complex. The absorption and luminescence spectra of the uranyl betainium complex have been studied in the solid state and dissolved in water, in acetonitrile, and in the ionic liquid betainium bistriflimide. The carboxylate groups remain coordinated to uranyl in acetonitrile and in betainium bistriflimide but not in water.
Resumo:
We undertook a two-stage genome-wide association study (GWAS) of Alzheimer's disease (AD) involving over 16,000 individuals, the most powerful AD GWAS to date. In stage 1 (3,941 cases and 7,848 controls), we replicated the established association with the apolipoprotein E (APOE) locus (most significant SNP, rs2075650, P = 1.8 x 10(-157)) and observed genome-wide significant association with SNPs at two loci not previously associated with the disease: at the CLU (also known as APOJ) gene (rs11136000, P = 1.4 x 10(-9)) and 5. to the PICALM gene (rs3851179, P = 1.9 x 10(-8)). These associations were replicated in stage 2 (2,023 cases and 2,340 controls), producing compelling evidence for association with Alzheimer's disease in the combined dataset (rs11136000, P = 8.5 x 10(-10), odds ratio = 0.86; rs3851179, P = 1.3 x 10(-9), odds ratio = 0.86).
Resumo:
The applicability of the Watson Hamiltonian for the description of nonlinear molecules—especially triatomic ones—has always been questioned, as the Jacobian of the transformation that leads to the Watson Hamiltonian, vanishes at the linear configuration. This results in singular behavior of the Watson Hamiltonian, giving rise to serious numerical problems in the computation of vibrational spectra, with unphysical, spurious vibrational states appearing among the physical vibrations, especially in the region of highly excited states. In this work, we analyze the problem and propose a simple way to confine the nuclear wavefunction in such a way that the spurious solutions are eliminated. We study the water molecule and observe an improvement compared with previous results. We also apply the method to the van der Walls molecule XeHe2.
Resumo:
Ever sceptical about the positivistic claims of ethnographic and so-called realist documentary, Johan van der Keuken’s film-making is the work of a curious, spontaneous and disorientated observer of the essential strangeness of both the foreign and the familiar, new landscapes and cities, experiences, and people. While there are various explicitly political and socially orientated films and themes across his work, it is those films and moments when what is being conveyed is a sense of him being somewhere liminal, being ‘in-between’ situations, cultures, styles and interpretations, reticent, uncertain but incorrigibly curious that constitute his most valuable contribution to documentary film aesthetics. Not surprisingly, such characteristics often come to the fore in those films where he tries to make sense of loss, the passing of lives and the legacies left behind. This article discusses questions of history and personal loss in a number of his films.