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81.
Wout De Nolf Jakub Jaroszewicz Roberto Terzano Ole Christian Lind Brit Salbu Bart Vekemans Koen Janssens Gerald Falkenberg 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(8):775
The performance of a combined microbeam X-ray fluorescence/X-ray powder diffraction (XRF/XRPD) measurement station at Hamburger Synchrotronstrahlungslabor (HASYLAB) Beamline L is discussed in comparison to that at European Synchrotron Radiation Facility (ESRF) ID18F/ID22. The angular resolution in the X-ray diffractograms is documented when different combinations of X-ray source, optics and X-ray diffraction detectors are employed. Typical angular resolution values in the range 0.3–0.5° are obtained at the bending magnet source when a ‘pink’ beam form of excitation is employed. A similar setup at European Synchrotron Radiation Facility beamlines ID18F and ID22 allows to reach angular resolution values of 0.1–0.15°. In order to document the possibilities and limitations for speciation of metals in environmental materials by means of Hamburger Synchrotronstrahlungslabor Beamline L X-ray fluorescence/X-ray powder diffraction setup, two case studies are discussed, one involved in the identification of the crystal phases in which heavy metals such as chromium, iron, barium and lead are present in polluted soils of an industrial site (Val Basento, Italy) and another involved in the speciation of uranium in depleted uranium particles (Ceja Mountains, Kosovo). In the former case, the angular resolution is sufficient to allow identification of most crystalline phases present while in the latter case, it is necessary to dispose of an angular resolution of ca. 0.2° to distinguish between different forms of oxidized uranium. 相似文献
82.
Peter Nockemann Dr. Ben Thijs Dr. Kyra Lunstroot Dr. Tatjana N. Parac‐Vogt Prof. Dr. Christiane Görller‐Walrand Prof. Dr. Koen Binnemans Prof. Dr. Kristof Van Hecke Dr. Luc Van Meervelt Prof. Dr. Sergey Nikitenko John Daniels Dr. Christoph Hennig Dr. Rik Van Deun Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(6):1449-1461
The dissolution process of metal complexes in ionic liquids was investigated by a multiple‐technique approach to reveal the solvate species of the metal in solution. The task‐specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare‐earth elements. The crystal structures of the compounds [Eu2(bet)8(H2O)4][Tf2N]6, [Eu2(bet)8(H2O)2][Tf2N]6?2H2O, and [Y2(bet)6(H2O)4][Tf2N]6 were found to consist of dimers. These rare‐earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C4mim][Tf2N] (C4mim=1‐butyl‐3‐methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, 1H, 13C, and 89Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X‐ray absorption fine structure) and HEXS (high‐energy X‐ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry. 相似文献
83.
84.
The complex derived from Taniaphos ligand 4 and CuBr*Me2S catalyzes the asymmetric addition of Grignard reagents to 3-bromopropenyl esters 1 to provide allylic esters 2 in high yields and high chemio-, regio-, and enantioselectivities. The work demonstrates that allylic asymmetric alkylation (AAA) can be done on substrates bearing a heteroatom at the gamma-position. The method is a practical route to chiral, nonracemic allylic alcohols. The use of functionalized substrates 1 or Grignard reagents leads to more complex products 2, which can be further manipulated as demonstrated in conversion to (S)-5-ethyl-2(5H)-furanone 6 and (S)-benzoic acid-cyclopent-2-enyl ester 7. 相似文献
85.
Zhang TG Zhao Y Song K Asselberghs I Persoons A Clays K Therien MJ 《Inorganic chemistry》2006,45(24):9703-9712
A series of conjugated (porphinato)zinc(II)-based chromophores structurally related to [5-(4-dimethylaminophenylethynyl)-15-(5-nitrothienyl-2-ethynyl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)]zinc(II) were synthesized using metal-catalyzed cross-coupling reactions involving [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II), [5-bromo-15-(4-dimethylaminophenylethynyl)-10,20-diarylporphinato]zinc(II), [5-(4-dimethylaminophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), and [5-(4-nitrophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), along with appropriately functionalized aryl, thienyl (or thiophenyl), thiazolyl, benzothiazolyl, and carbazolyl precursors. The linear and nonlinear optical properties of these asymmetrically 5,15-substitued-(10,20-diarylporphinato)zinc(II) chromophores that bear either 2-(9H-carbazol-9-yl)-thiophen-5-yl-ethynyl, 4-dimethylaminophenylethynyl, or 2-(N,N-diphenylamino)thiophen-5-yl-ethynyl electron-releasing groups and an electron-withdrawing group selected from 2-formyl-thiophen-5-yl-ethynyl, 2-(2,2-dicyanovinyl)-thiophen-5-yl-ethynyl, 4-nitrophenylethynyl, 6-nitrobenzothiazol-2-yl-ethynyl, or 5-nitrothiazol-2-yl-ethynyl are reported. The dynamic hyperpolarizabilities of these compounds were determined from hyper-Rayleigh light scattering measurements carried out at a fundamental incident irradiation wavelength (lambda(inc)) of 1300 nm; these measured beta1300 values ranged from 690 --> 1400 x 10(-30) esu. These data (i) show that these neutral dipolar molecules express substantial beta1300 values, (ii) highlight that reductions in the magnitude of the aromatic stabilization energy of (porphinato)metal-pendant arylethynyl groups have a significant impact upon the magnitude of the molecular hyperpolarizability, and (iii) provide insights into advantageous design modifications for closely related structures having potential utility in long-wavelength electrooptic applications. 相似文献
86.
Howell GP Fletcher SP Geurts K ter Horst B Feringa BL 《Journal of the American Chemical Society》2006,128(46):14977-14985
Herein, we report efficient acyclic stereocontrol in tandem 1,4-addition-aldol reactions triggered by catalytic asymmetric organometallic addition. Grignard reagents add to alpha,beta-unsaturated thioesters in a 1,4-fashion and the resulting magnesium enolates are trapped with aromatic or aliphatic aldehydes. The process provides a range of tandem products bearing three contiguous stereocenters with excellent control of relative and absolute stereochemistry. The various diastereomeric products have been fully characterized using single-crystal X-ray analysis and the origins of stereocontrol in this tandem protocol are discussed. The versatility and efficiency of this methodology are demonstrated in the first catalytic asymmetric synthesis of (-)-phaseolinic acid with 54% overall yield via a short and concise route. 相似文献
87.
88.
Van Deun R Fias P Nockemann P Van Hecke K Van Meervelt L Binnemans K 《Inorganic chemistry》2006,45(26):10416-10418
The unique absorption properties of the 9-hydroxyphenalen-1-one (HPHN) ligand have been exploited to obtain visible-light-sensitizable rare-earth complexes in 1:3 and 1:4 metal-to-ligand ratios. In both stoichiometries (1:3, tris, Ln(PHN)3; 1:4, tetrakis, A[Ln(PHN)4], with Ln being a trivalent rare-earth ion and A being a monovalent cation), the complexes of Nd(III), Er(III), and Yb(III) show typical near-infrared luminescence upon excitation with visible light with wavelengths up to 475 nm. The X-ray crystal structures of the tris complexes show solvent coordination to the central rare-earth ion, whereas in the tetrakis complexes, the four PHN- ligands form a protective shield around the central ion, preventing small solvent molecules from coordinating to the rare-earth ion, at least in the solid state. 相似文献
89.
Wu T Nauwelaerts K Van Aerschot A Froeyen M Lescrinier E Herdewijn P 《The Journal of organic chemistry》2006,71(15):5423-5431
A method has been developed for the synthesis of bisheaded nucleosides with thymine and adenine base moieties. We have demonstrated that, when incorporated in oligonucleotides, extrahelical A-T base interactions are possible when the bisheaded nucleosides are positioned in opposite strands of the duplex and are separated from each other by one regular base pair. 相似文献
90.
Surface-stabilized orthoconic antiferroelectric liquid crystals (OAFLCs) have a director tilt of theta = 45 degrees and are, with no field applied, negatively uniaxial with the optic axis perpendicular to the cell substrates. We demonstrate that OAFLCs can be utilized to achieve lossless phase modulation with three almost equidistant phase levels. This turns out to be true also for polymer-stabilized OAFLCs, where the polymer network increases the switching speed of the device without affecting the phase modulation appreciably. 相似文献