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31.
N. S. Nesterenko F. Thibault-Starzyk V. Montouilliout V. V. Yushchenko C. Fernandez J.-P. Gilson F. Fajula I. I. Ivanova 《Kinetics and Catalysis》2006,47(1):40-48
A new approach to the evaluation of the accessibility of acid sites in microporous/mesoporous materials is developed and tested
using a series of dealuminated mordenites. This approach is based on an IR-spectroscopic study of the consecutive adsorption
of substituted alkylpyridines (pyridine, 2,4,6-trimethylpyridine, and 2,4,6-triethylpyridine) and carbon monoxide. This method
allowed us to determine the strength and number of acid sites with various degrees of accessibility. The adsorption of 2,4,6-triethylpyridine
on various types of materials is studied. The extinction coefficients of alkylpyridines are determined using a McBain balance
placed in a cell for IR-spectroscopic measurements.
Original Russian Text N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.-P. Gilson,
F. Fajula, I.I. Ivanova, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 45–53. 相似文献
32.
Douglas R. Hurst Kristen L. French April J. Angel Angela R. Williams Mary E. Rampey Tina S. Guion Kam W. Chan Camille M. Kassis Shannon L. Studer Martinez Charles F. Beam 《Journal of heterocyclic chemistry》1998,35(6):1357-1359
Several acetoacetanilides were trilithiated in excess lithium diisopropylamide, and the resulting polylithiated intermediates were regioselectively condensed with lithiated methyl salicylates followed by acid cyclization to substituted 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides (benzopyranone-2-acetamides). 相似文献
33.
Joan Albaigés Josep M. Bayona Pilar Fernandez Joan Grimalt Antoni Rosell Rafel Simó 《Mikrochimica acta》1991,104(1-6):13-27
An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon. 相似文献
34.
Hydrodynamic properties for a class of nondiffusive particle systems are investigated. The method allows one to study local equilibria for a class of asymmetric zero-range processes, and applies as well to other models, such as asymmetric simple exclusion and misanthropes. Attractiveness is an essential ingredient. The hydrodynamic equations present shock wave phenomena. Preservation of local equilibrium is proven to hold away from the shocks. The problem of breakdown of local ergodicity at the shocks, which was investigated by D. Wick in a particular model, remains open in this more general setup. 相似文献
35.
A. Caubet A. Labarta R. Rodríguez A. Fernandez E. Molins V. Moreno J. Tejada 《Hyperfine Interactions》1986,28(1-4):773-776
By means of57Co Mössbauer emission spectroscopy and magnetic susceptibility measurements, the local symmetries and electronic structure of the Co(II) ions in the Co-5IMO and Co-5GMP complexes in the hydrated and dehydrated forms have been determined. 相似文献
36.
Rüdiger O Abad JM Hatchikian EC Fernandez VM De Lacey AL 《Journal of the American Chemical Society》2005,127(46):16008-16009
The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation. 相似文献
37.
Gálvez-Ruano E Iriepa-Canalda I Morreale A Lipkowitz KB 《Journal of computer-aided molecular design》1999,13(1):57-68
We have derived a model of the nicotinic acetylcholine binding site. This was accomplished by using three known agonists (acetylcholine, nicotine and epibatidine) as templates around which polypeptide side chains, found to be part of the receptor cavity from published molecular biology studies, are allowed to flow freely in molecular dynamics simulations and mold themselves around these templates. The resulting supramolecular complex should thus be a complement, both in terms of steric effects as well as electronic effects, to the agonists and it should be a good estimation of the true receptor cavity structure. The shapes of those minireceptor cavities equilibrated rapidly on the simulation time scale and their structural congruence is very high, implying that a satisfactory model of the nicotinic acetylcholine binding site has been achieved. The computational methodology was internally tested against two rigid and specific antagonists (dihydro--erytroidine and erysoidine), that are expected to give rise to a somewhat differently shaped binding site compared to that derived from the agonists. Using these antagonists as templates there were structural reorganizations of the initial receptor cavities leading to distinctly different cavities compared to agonists. This indicates that adequate times and temperatures were used in our computational protocols to achieve equilibrium structures for the agonists. Overall, both minireceptor geometries for agonists and antagonists are similar with the exception of one amino acid (ARG209). 相似文献
38.
Lydia J. Martinez Robert H. Sik Colin F. Chignell† 《Photochemistry and photobiology》1998,67(4):399-403
The fluoroquinolone antibacterial agents possess photo-sensitizing properties that lead to phototoxic responses in both human and animal subjects. The phototoxicity order reported in humans is: fleroxacin > lomefloxacin, pefloxacin > ciprofloxacin ? enoxacin, norfloxacin and ofloxacin. Studies both in vivo and in vitro have related this phototoxicity to the generation of reactive oxygen species including hydrogen peroxide and the hydroxyl radical. We determined the quantum yields of singlet oxygen generation (φΔ,) by detection of the singlet oxygen (1O2) luminescence at 1270 tun for several fluoroquinolones, naphthyridines and other structurally related compounds. All the fluoroquinolones examined have low φΔ values ranging from 0.06 to 0.09 in phosphate buffer at pD 7.5. We also determined the 1O2 quenching constants for these compounds and their values were on the order of 106M?1 s1, except for lomefloxacin whose rate constant was 1.8 × 107M?1 s?1. The φΔ values were significantly decreased in a solvent of lower polarity such as methanol (0.007 ≤φΔ≤ 0.02). The production of 1O2 by these antibiotics did not correlate with the order reported for their phototoxicity. We also measured the photogeneration (λ > 300 nm) of superoxide by these antibacterials in dimethylsulfoxide using electron paramagnetic resonance and the spin trap 5,5-dimethyl-l-pyrroiine N-oxide. Although there is not a one-to-one correspondence between the relative rates of superoxide generation and the phototoxicity ranking of the fluoroquinolones, the more phototoxic compounds tended to produce superoxide at a faster rate. Nevertheless, the magnitudes of the observed differences do not appear sufficient to explain the range of fluoroquinolone phototoxicity potencies in human and animal subjects in general and the high activity of fleroxacin and lomefloxacin in particular. For these latter drugs the photoinduced loss of the F8 atom as fluoride and the concomitant generation of a highly reactive carbene at C-8 provide a more plausible mechanism for their potent phototoxic and photocarcinogenic properties. 相似文献
39.
40.
Masip I Pérez-Payá E Messeguer A 《Combinatorial chemistry & high throughput screening》2005,8(3):235-239
N-Alkylglycine oligomers (peptoids) constitute a family of non-natural peptidomimetics attractive for the early drug discovery process because of their physicochemical features, easy of adaptation to combinatorial chemistry approaches and their proteolytic stability. Consequently, peptoid libraries have found application for discovering hits against a wide diversity of pharmaceutical targets, among which different examples of antibacterials are found. In the present work, research efforts addressed towards the identification of peptoids as antibacterial agents are discussed. 相似文献