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51.
New mesoporous niobium oxides with 5, 10, and 15 mol% vanadium(V) doped into the walls of the structure were synthesized by the ligand-assisted templating method with an octadecylamine template. These materials were characterized by XRD, XPS, EPR, elemental analysis, and nitrogen adsorption before being treated with excess bis(benzene)chromium to give new composites with an organometallic phase in the walls. All materials were also characterized by EPR, XRD, nitrogen adsorption, XPS, SQUID magnetometry, and elemental analysis. The materials with higher percentages of vanadium absorbed more bis(benzene)chromium, because this process depends largely on the electron transfer between the organometallic and the walls of the mesostructure and vanadium(V) is a stronger oxidant than niobium(V). Conductivity studies on these materials revealed that the ratio of Cr(0) to Cr(l) in the pores was more important than the absolute Cr loading level in governing electron transport properties but that increasing the V content led to more insulating behavior regardless of the Cr concentration. Solid-state 2H NMR studies on perdeuteriobenzene analogues of these composites showed the presence of the neutral and cationic Cr species in different ratios depending on the loading. Tumbling of these species was also slow on the NMR time scale, indicating that the charge-carrying Cr species are not rapidly moving through the pore channels of the mesostructure. This suggests that the walls of the structure may play a key role in charge transfer in these composites, contrary to what was previously believed. 相似文献
52.
Boudjahem AG Monteverdi S Mercy M Bettahar MM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(1):208-213
We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase. 相似文献
53.
Michel Petitjean 《Journal of computational chemistry》1995,16(1):80-90
The geometric molecular dissimilarity between two molecules is defined as the difference between the volume of their union minus the volume of their intersection. This dissimilarity has the mathematical properties of a distance. This distance is minimized under all rotations and translations using a discrete Broyden, Fletcher, Goldfarb & Shanno (B.F.G.S.) algorithm. The optimal geometric superimposition of saxitoxin and tetrodotoxin is discussed. © 1995 by John Wiley & Sons, Inc. 相似文献
54.
J.Georges Duboudin Michel Petraud Max Ratier Bruno Trouve 《Journal of organometallic chemistry》1985,288(1):C6-C8
Flash pyrolysis of alkyltributyltin acetates, at high temperatures (600–850° C) under a moderate vacuum provides a convenient route to vinyltin derivatives. 相似文献
55.
Mechanical and physico-chemical characterization of cyclodextrin finished polyamide fibers 总被引:2,自引:0,他引:2
Yassine El Ghoul Bernard Martel Michel Morcellet Christine Campagne Ahmida El Achari Sadok Roudesli 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):47-52
We present the study of the cyclodextrin (CDs) finishing of polyamide fibers (PA) by means of citric acid (CTR) as crosslinking agent. We observed that the mode of grafting happened by the formation of a crosslinked polymer formed between CTR and CDs. This polymer physically adhered to the fibers network and was resistant to hot water washings. Modified fibers were characterized by evaluating the contact angle with a polar liquid and by studying the hysteresis of damping of PA fibers (Cahn balance) with various grafting rates and by studying the absorptivity of grafted fabrics via the technique of the posed drop (Digidrop® instrument). Then a mechanical characterization of the PA fabrics grafted with various proportions of CDs was accomplished, by traction and tear tests by using a tensile-test bench Lohmergy. Finally a topographic study of PA grafted surfaces was approached by atomic force microscopy (AFM and LFM; contact and non-contact mode) which permitted to evaluate the roughness and the chemical heterogeneity of the grafted surfaces. 相似文献
56.
Jean Michel Brunel 《Tetrahedron》2007,63(18):3899-3906
A new and efficient mild Pd/P(t-Bu)3 catalyst for selective reduction of various alkenes under transfer hydrogen conditions has been developed leading to the corresponding saturated derivatives in chemical yields varying from 65 to 98%. Mechanistic rationale of this reaction has been also demonstrated. 相似文献
57.
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
58.
Interchange reactions involving esters were used in reactive processing with a view to obtaining polymer blends with stabilized morphology. Dibutyltinoxide (DBTO) appeared to be an excellent catalyst for these reactions. In fact, it was shown that the true catalytic entity is a dimeric alkoxy, acyloxy distannoxane entity formed in situ, during processing, by the reaction of the DBTO with the polymer ester groups. This compound was first obtained with model esters and characterized by multinuclear NMR analysis (1H, 13C, 119Sn). The catalytic efficiency of the in situ polymeric distannoxane was compared with other added parent distannoxanes. Later on – still with model compounds – ligand exchanges at the tin sites were investigated and it was shown that these exchanges are not essential to the catalyst activity, but when they take place it increases the catalytic efficiency. Then, this type of catalysis was successfully used for interchange reactions in reactive extrusion of different polymer blends, some applications are briefly presented. To cite this article: M.-F. Llauro and A. Michel, C. R. Chimie 9 (2006). 相似文献
59.
Taglialatela-Scafati O Deo-Jangra U Campbell M Roberge M Andersen RJ 《Organic letters》2002,4(23):4085-4088
The known antimitotic agent eleutherobin and the briarane diterpenoids erythrolides A and B have been isolated from cultured specimens of Erythropodium caribaeorum in amounts comparable to those reported from wild-harvested reef animals. The novel diterpenoid aquariolide A, having an unprecedented highly rearranged carbon skeleton (named aquariane), has also been found. The aquariane skeleton can be formally derived from the briarane skeleton by sequential di-pi-methane and vinyl-cyclopropane rearrangements. [structure: see text] 相似文献
60.
Abdeloihid Mellouki Robert Georges Michel Herman Deanne L. Snavely Svetlana Leytner 《Chemical physics》1997,220(3):443-322
We have recorded the infrared absorption spectrum of pyrrole at 0.005 cm−1 spectral resolution using a Fourier transform interferometer. The rotational analysis of the fundamental N---H stretch (110) at 3530.811343(82) cm−1 was performed. A set of 13 upper state rovibrational parameters was determined, allowing the 2715 assigned rovibrational lines to be reproduced with a standard deviation of 1.3 10−3 cm−1. An attempt to record the fundamental band under slit-jet conditions is reported. The role of hot bands accompanying the series of the N---H stretch excitation is investigated. Effective vibrational parameters — ω01, X011, Y111, X1,24 — are obtained. The lower level in the hot band series is unambiguously identified as the V24 = 1 level, by retrieving X1,24 independently, from other spectral data. The observation of the complex band pattern accompanying the N---H series in the higher overtone range is discussed with the help of new data, recorded around the 150 band at different temperatures using intracavity laser optoacoustic spectroscopy. 相似文献