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21.
Two synthetic routes to a novel class of sterically overcrowded alkenes, bithioxanthylidene crown ethers 1, are described. The 1H spin-lattice relaxation times (T1) of the crown ethers as well as those of the corresponding complexes with Li+, Na+, K+, Rb+ and Cs+ in CDCl3 were measured and the results were interpreted in terms of complexation affinities. 相似文献
22.
Fabien Fontaine Evan Bolton Yulia Borodina Stephen H Bryant 《Chemistry Central journal》2007,1(1):12-14
Background
Large chemical databases require fast, efficient, and simple ways of looking for similar structures. Although such tasks are now fairly well resolved for graph-based similarity queries, they remain an issue for 3D approaches, particularly for those based on 3D shape overlays. Inspired by a recent technique developed to compare molecular shapes, we designed a hybrid methodology, alignment-recycling, that enables efficient retrieval and alignment of structures with similar 3D shapes. 相似文献23.
24.
Atomic hydrogen electrosorption is reported at crystallite sites of polyacrylate-capped Pt nanoparticles (d = 2.5 +/- 0.6 nm), by assembling nanostructured electrodes of polyacrylate-Pt nanocrystallites layer-by-layer in a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). Cyclic voltammetry in 1 M H2SO4 revealed a strongly adsorbed hydrogen state and a weakly adsorbed hydrogen state assigned to adsorption at (100) and (110) sites of the modified nanocrystallites, respectively. Resolving hydrogen adsorption states signifies that surface capping by the carboxylate groups is not irreversibly blocking hydrogen adsorption sites at the modified Pt nanoparticle surface. Adsorption peak currents increased with increasing the number of layers up to 16 bilayers, indicating the feasibility of nanoparticle charging via interparticle charge hopping and the accessibility of adsorption states within the thickness of the nanoparticle/polyelectrolyte multilayers. Despite similarity in hydrogen adsorption in the cyclic voltammorgrams in 1 M H2SO4, negative shifts in adsorption potentials were measured at the nanocrystallite Pt-polyelectrolyte multilayers relative to a polycrystalline bulk Pt surface. This potential shift is attributed to a kinetic limitation in the reductive hydrogen adsorption as a result of the Pt nanoparticle surface modification and the polyelectrolyte environment. 相似文献
25.
Vanderperren H Van Wouwe N Behets S Windal I Van Overmeire I Fontaine A 《Talanta》2004,63(5):1277-1280
Polyhalogenated aromatic hydrocarbons, such as polychlorinated dibenzo-p-dioxins are a large and diverse group of environmental pollutants. Their tendency to accumulate in the food chain and their toxicity make monitoring necessary. The reference analysis method is laborious and very expensive, therefore cheap and rapid bioassays have been developed. The chemical-activated luciferase bioassay (CALUX) bioassay uses a recombinant cell line, which responds to dioxins and dioxin-like molecules with Ah receptor (AhR)-dependent induction of firefly luciferase in a dose related response. The CALUX was tested for its use in the screening of feed. Aliquots of 20 g of enriched feed were extracted with a toluene:methanol mixture (20:4 v/v) and extracts were defatted on 33% H2SO4 silica columns and purified on carbon columns. Only the dioxin and furan fraction was analysed, the PCB fraction was discarded. The precision of the method is acceptable and in compliance with an R.S.D. <30% as suggested for cell-based bioassays in the Commission Directive 2002/70/EC of July 2002. The results evidence good agreement between TEQ-values obtained by either CALUX or GC–HRMS. The method is now routinely in use for a feed screening programme designed by the Federal Agency for the Safety of the Food chain. Approximately, 25 samples are analysed weekly. From the obtained results approximately 10% was confirmed by GC–HRMS. The false positive ratio is 1% and no false negatives were found, making the use of the CALUX technology advantageous. 相似文献
26.
Mikkelsen Ø Skogvold SM Schrøder KH Gjerde MI Aarhaug TA 《Analytical and bioanalytical chemistry》2003,377(2):322-326
Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L–1 (r2=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r2=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H2SO4 to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed. 相似文献
27.
Vincent Lapinte Laurent Fontaine Vronique Montembault Irne Campistron Danile Reyx 《Journal of molecular catalysis. A, Chemical》2002,190(1-2):117-129
ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined. 相似文献
28.
Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P2(1)/c with a = 10.157(3) A, b = 14.038(9) A, c = 16.335(2) A, beta = 99.73(2) degrees, and Z = 4 for 1a and with a = 10.107(9) A, b = 13.994(16) A, c = 15.996(34) A, beta = 99.61(12) degrees, and Z = 4 for 1b. The coordinated water molecule is hydrogen bonded to both BF4(-) anions. Reaction of 1a,b with pyridine (py) afforded the related tris(pyridine) complexes [(C5Me5)M(eta1-(N)-py)3][BF4]2 (M = Rh, Ir) (2a,b). Complex 2b was characterized by X-ray crystallography, monoclinic space group P2(1)/c with a = 8.665(3) A, b = 19.687(7) A, c = 18.408(5) A, beta = 94.17(3) degrees, and Z = 4. Moreover, we prepared the novel neutral compounds (C5Me5)M(eta2-NO3)(eta1-NO3) (M = Rh, Ir) (4a,b) where the anions are bonded to the metal center instead of a coordinating solvent as confirmed by X-ray study on the iridium complex 4b. The latter crystallizes in the orthorhombic space group Pcab with a = 13.032(4) A, b = 14.370(11) A, c = 14.839(18) A, and Z = 8. 相似文献
29.
Guryca V Pacáková V Tlust'áková M Stulík K Michálek J 《Journal of separation science》2004,27(13):1121-1129
Topography and thickness of hydrophilic polymer coatings of fused-silica capillaries for capillary electrophoresis (CE) were investigated using atomic force microscopy (AFM), scanning electron microscopy (SEM), and profilometry. Three hydrogels, poly(2-hydroxyethyl methacrylate) [poly(HEMA)], poly(diethylene glycol monomethacrylate) [poly(DEGMA)], and poly(triethylene glycol monomethacrylate) [poly(TEGMA)], were deposited using two procedures, either by simple physical sorption of the polymers, or by derivatization of the capillary wall surface with glycidyl methacrylate (EPMA) followed by polymerization of the appropriate monomers. The performance of the modified capillaries was tested under CE conditions (decrease in the electroosmotic flow, EOF dependence on pH, separation of milk and standard proteins). It has been found that the most important property of the polymer coating is its thickness, whereas its topography and the degree of its hydrophobicity are less significant. Film deposition by physical adsorption is preferable to polymerization on the derivatized surface. 相似文献
30.
Hourdin M Gouhier G Gautier A Condamine E Piettre SR 《Journal of combinatorial chemistry》2005,7(2):285-297
Ten cross-linked polystyrene-supported, protected chiral amines featuring both a spacer, comprising from 5 to 15 atoms, and a fluorinated linker have been successfully prepared. The development of the monitoring technique by gel-phase 19F NMR spectrometry on cross-linked polystyrene derivatives proved to be of high value in four steps of the process, as shown by the comparison of data gathered from both a classic NMR spectrometer and elemental analysis. Gel-phase 19F NMR spectrometry, thus, constitutes a useful technique that complements IR and 13C NMR spectrometries for the qualitative monitoring of reactions. In addition, quantitative determination of the conversion in a given transformation is possible, provided that 19F chemical shifts of the substrate and the product be different enough (Deltadelta>base width), as illustrated by the Mitsunobu coupling process (16-->17). The technique is nondestructive, and the samples used to monitor the reactions may be returned to the reaction medium. Deprotection of the above amines was achieved and furnished eight of the final resins in good to acceptable purity for future applications. 相似文献