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71.
[reaction: see text]. Rate constants for hydrogen abstraction from phenols by a prefluorescent-TEMPO probe are reported. The nitroxide is employed as a potential model of peroxyl radicals. The probe works by nitroxide suppression of the fluorescence of the chromophore. The fluorescence is restored when the nitroxide abstracts a hydrogen atom to produce the diamagnetic hydroxylamine. The phenols studied in this project exhibited rate constants between 0.003 and 0.2 M(-1) s(-1). A deuterium isotope effect of 10 for TROLOX confirms that the mechanism is dominated by hydrogen transfer. 相似文献
72.
Andrea Rodriguez Loriett Cartaya Alexis Maldonado Edgar Marquez José R. Mora Tania Cordova 《Molecular physics》2017,115(14):1624-1632
The study on the mechanism of the gas-phase elimination or thermal decomposition kinetics of 2, 2-dimethyl-3-butenal has been carried out by using theoretical calculation at MP2, combined ab initio CBSQB3 and DFT (B3LYP, B3PW91, MPW1PW91, PBEPBE, PBE1PBE, CAMB3LYP, M06, B97d) levels of theory. A good reasonable agreement between experimental and calculated parameters was obtained by using CAMB3LYP/6-311G(d,pd) calculations. The contrasted calculated parameters against experimental values suggested decarbonylation reaction to proceed through a concerted five-membered cyclic transition state type of mechanism, involving the hydrogen transfer from the carbonyl carbon to the gamma carbon, consistent with observed kinetic isotope effect. The breaking of alpha carbon–carbonyl carbon bond to produce carbon monoxide is 50% advanced in the transition state. The reaction mechanism may be described as a concerted moderately non-synchronous process. Examination of the Atoms in Molecules (AIM) analysis of electron density supports the suggested mechanism. 相似文献
73.
Alexis Marin 《Mathematische Annalen》1987,278(1-4):211-217
Sans résuméDédié à Friedrich Hirzebruch 相似文献
74.
E. Alexis 《Analytical and bioanalytical chemistry》1935,103(11-12):452-452
75.
We present a nondestructive and noncontact extensometry technique, which has been developed in order to study the behavior of different materials such as polycarbonate, araldite, urethane, etc. A spectral analysis of a crossed grating marked on the surface of a specimen and recorded by a charge coupled device camera is presented. The procedure is based on the use of a bidimensional fast Fourier transform algorithm coupled with an interpolation process. It leads to the accurate determination of frequencies. Numerical simulations have been made to evaluate the strain sensitivity; it depends on both the initial phase and the number of cycles characterizing the grid. Theoretically, the strain sensitivity can reach 10-5 in best cases, but practically it is notbetter than 10-4. Several applications on different materials are presented: polyurethane, paper and cloth. 相似文献
76.
Peter Barker Alexis Bishop Halina Rubinsztein-Dunlop 《Applied physics. B, Lasers and optics》1997,64(3):369-376
A novel flow-tagging technique is presented which was employed to measure gas velocities in the free stream of a shock tube.
This method is based on the laser spectroscopic techniques of Laser-Enhanced Ionisation (LEI) and Laser-Induced Fluorescence
(LIF). The flow in the shock tube is seeded with small amounts of sodium, and LEI is used to produce a substantial depletion
of neutral sodium atom concentration in a well-defined region of the flow, by using two wavelength-resonance excitation and
subsequent collisional ionisation. At a specific time delay, single-laser-pulse planar LIF is utilised to produce a two-dimensional
(2-D) inverse image of the depleted tagged region downstream of the flow. By measuring the displacement of the tagged region,
free stream velocities in a shock tube were determined. Large variations in the concentration of sodium seeded into the flow
were observed and even in the presence of these large variations accurate free-stream velocity measurements were obtained.
The experimentally determined value for velocity compares very well with the predicted velocity.
Received: 25 March 1996/Revised version: 8 July 1996 相似文献
77.
The effects of Na+ ions on the physicochemical properties and catalytic activity of CoMo/-Al2O3 hydrodesulfurization catalysts prepared by inverse impregnation has been studied. The catalytic activity was found to be almost independent of the priority of impregnation, it is correlated with the distribution of promoter species in the oxidic precursors as well as with the selectivity of the catalysts. The Na doping of the support brings about a progressive decrease in the catalytic activity due to the partial scavenging of MoVI by Na+ to form Na2MoO4.
Na+ - . CoMo/-Al2O3, . . , . , MoVI Na+, Na2MoO4.相似文献
78.
Leleu S Penhoat M Bouet A Dupas G Papamicaël C Marsais F Levacher V 《Journal of the American Chemical Society》2005,127(45):15668-15669
A new and unprecedented exploitation of quinolinium thioester salts 2 in peptide bond formation is reported. These synthetic tools were assessed during the preparation of a number of dipeptides 3a-f obtained in good yields with complete stereochemical integrity. A sequential mechanism related to a prior amine capture strategy is well-established. Additionally, a tripeptide 3g was prepared according to a "safety-catch" approach, thus demonstrating the important potential of these new synthetic tools in the design of new safety-catch linkers exploitable in Solid-Phase Peptide Synthesis (SPPS). 相似文献
79.
80.