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101.
Schimmel HG Huot J Chapon LC Tichelaar FD Mulder FM 《Journal of the American Chemical Society》2005,127(41):14348-14354
The reaction of hydrogen gas with magnesium metal, which is important for hydrogen storage purposes, is enhanced significantly by the addition of catalysts such as Nb and V and by using nanostructured powders. In situ neutron diffraction on MgNb(0.05) and MgV(0.05) powders give a detailed insight on the magnesium and catalyst phases that exist during the various stages of hydrogen cycling. During the early stage of hydriding (and deuteriding), a MgH(1< x < 2) phase is observed, which does not occur in bulk MgH(2) and, thus, appears characteristic for the small particles. The abundant H vacancies will cause this phase to have a much larger hydrogen diffusion coefficient, partly explaining the enhanced kinetics of nanostructured magnesium. It is shown that under relevant experimental conditions, the niobium catalyst is present as NbH(1). Second, a hitherto unknown Mg-Nb perovskite phase could be identified that has to result from mechanical alloying of Nb and the MgO layer of the particles. Vanadium is not visible in the diffraction patterns, but electron micrographs show that the V particle size becomes very small, 2-20 nm. Nanostructuring and catalyzing the Mg enhance the adsorption speed that much that now temperature variations effectively limit the absorption speed and not, as for bulk, the slow kinetics through bulk MgH(2) layers. 相似文献
102.
Clémence Guillaume Jacques Le Calvé Iliana Dimicoli Michel Mons 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1994,32(1):157-165
The intensity distribution of benzene+-Arn cluster ions formed by laser ionization of neutral clusters has been investigated: two main intensity anomalies (magic numbers atn=20 and 45) have been observed in the 15–60 size range. The evaporation dynamics of these species in the 2–50 microsecond time window following ionization has been studied using the electrostatic mirror of a reflectron time-of-flight mass spectrometer as a kinetic energy analyser capable to distinguish parent and daughter ions. The magic numbers are interpreted in terms of size dependent evaporation behaviors: beyondn=20, a sudden decrease of the evaporation energy is observed; in then=45–47 size range, the magic number is accounted for by the specific dynamics of then=46 and 47 clusters, in particular the possible loss of two argon atoms forn=47 within the experimental time window. These results and their implications on the cluster structure are discussed in the light of the evaporative ensemble model and compared to the evaporation characteristics of similar species, in particular the neat rare gas clusters. 相似文献
103.
A unique process of chemical oxidation polymerization of aniline using manganese dioxide (MnO2) as the oxidizing agent in an aqueous medium is described. The reaction between aniline and MnO2 follows a mechanism by which the organic monomer is oxidized while the metal oxide undergoes reductive dissolution. The effects of the amount of oxidizing agent and aniline, pH and temperature of the reactive system, type of acid on the yield and conductivity of polyaniline are discussed. The resulting polyaniline was characterized by [R and UV-Vis spectrometry. Polyaniline with a conductivity of 12.5 S/cm was obtained using 0.033 tool of aniline oxidized by 0.023 tool MnO2 in the presence of 100 mL of 2.7 mol/L HCI at 25℃ for 4 h. 相似文献
104.
The silver nitrate assisted cyclization of the entitled diols leads, depending on the substitution of the allenic linkage, specifically to dihydropyranes , when R is alkyl or to an equimolecular mixture of and its tetrahydrofuranyl isomer when R is hydrogen. 相似文献
105.
Optimal performance laminar chromatography and automated multiple development chromatography are relatively recent techniques of planar chromatography that can be applied with success in plant material analysis. Therefore, these methods are used to study plant extracts and constituents belonging to different chemical classes of secondary metabolism: heterocyclic oxygen compounds (coumarins, flavonoids, and anthocyanins), alkaloids and quaternary ammonium salts, cannabinoids, essential oils, ginsenosides, and cardiac heterosides. Generally, the results obtained with these methods are good, and in most cases they compare with those of thin-layer chromatography. 相似文献
106.
Alphonse Ekouya Raymond Calas Jacques Dunogues Claude Biran Norbert Duffaut 《Journal of organometallic chemistry》1979,177(1):137-144
Aliphatic saturated amides treated with Me3SiCl/Li/THF were found to react in two ways. Either alkoxysilanes, mono- or di-silylated at the functional carbon, or C-silylated amines were obtained dependent of the original amide structure and the experimental conditions. (Me3Si)2CHN(SiMe3)2 exhibited Physicochemical properties that are particular for hindered rotation about the CN bond. A general mechanism is proposed to explain these results. 相似文献
107.
Christians Ferradini Jacques Foos Chantal Houee Jacques Pucheault 《Photochemistry and photobiology》1978,28(4-5):697-700
Abstract— In order to obtain a better understanding of the kinetics of the Haber-Weiss reaction
often proposed as a source of OH radicals, we have measured the decomposition rate of H2 O2 in aqueous solutions by y rays and for different pH values. This decomposition proceeds by a chain reaction involving the preceding one as the propagating step.
The rate constant found is to be
相似文献
often proposed as a source of OH radicals, we have measured the decomposition rate of H
The rate constant found is to be
相似文献
108.
Structural basis for thrombin activation of a protease-activated receptor: inhibition of intramolecular liganding 总被引:3,自引:0,他引:3
Seeley S Covic L Jacques SL Sudmeier J Baleja JD Kuliopulos A 《Chemistry & biology》2003,10(11):1033-1041
Protease-activated G protein-coupled receptors (PAR1-4) are tethered-ligand receptors that are activated by proteolytic cleavage of the extracellular domain (exodomain) of the receptor. PAR1, the prototypic member of the PAR family, is the high-affinity thrombin receptor of platelets and vascular endothelium and plays a critical role in blood coagulation, thrombosis, and inflammation. Here, we describe the solution structure of the thrombin-cleaved exodomain of PAR1. The side chains of a hydrophobic hirudin-like (Hir) sequence and adjacent anionic motif project into solution. Docking of the exodomain Hir sequence to exosite I of thrombin reveals that the tethered ligand in the cleaved exodomain bends away from thrombin, leaving its active site available to another large macromolecular substrate. The N-terminal ligand is longer than anticipated and forms an intramolecular complex with a region located in the C terminus of the exodomain. Mutational analysis confirmed that this C-terminal region is a ligand binding site for both intra- and intermolecular ligands. A lipidated-ligand binding site peptide was found to be an effective inhibitor of thrombin-induced platelet aggregation. 相似文献
109.
Baffert C Collomb MN Deronzier A Pécaut J Limburg J Crabtree RH Brudvig GW 《Inorganic chemistry》2002,41(6):1404-1411
Two new terpyridine dimanganese oxo complexes [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(CF(3)CO(2))(2)](+) (3) and [Mn(2)(III,III)(mu-O)(terpy)(2)(CF(3)CO(2))(4)] (4) (terpy = 2,2':6,2' '-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn(2)(III,IV)(mu-O)(2)(terpy)(2)(H(2)O)(2)](3+) (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF(3)CO(2)(-) ligands on each manganese adopt a cis geometry to each other; one CF(3)CO(2)(-) is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF(3)CO(2)(-) have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH(3)CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH(3)CN solution into the mixed-valent complex 3 and the mononuclear complex [Mn(II)(terpy)(2)](2+) (2), thereby preventing the observation of its electrochemical behavior. 相似文献
110.
Titanates de cuivre substitués à structure bixbyite: Les composés Cu1−xTi1−xFe2xO3 (0.15 ≤ x ≤ 0.33)
A new bixbyite family, Cu1?xTi1?xFe2xO3 (0.15 ≤ x ≤ 0.33) has been synthesized and characterized. The unit cell is cubic: a ~ 9.40Å. The X-ray powder diffraction study shows up an isotypism with the (Fe, Mn)2O3 compounds. There is a disordered distribution of CuII, TiIV, and FeIII over the two cyrstallographic sites: PI and PII. PII is highly distorted (two long MO distances) by the Jahn-Teller effect of CuII. The bixbyite structure is described in terms of polyhedra arrangement, as a particular case of the CM2O3 family. The cation packing is discussed in relation with the existence of the bixbyite structure for the Cu1?xTi1?xFe2xO3 compounds. The electrical properties (σ ~ 10?5(Ω cm)?1 for x = 0.286 at room temperature) show an electron conduction with probably a hopping mechanism. 相似文献