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11.
α-Oxo-carboxylic acids undergo photo-oxidative decarboxylation from both C-1 and C-2 positions, and reaction does not involve singlet oxygen: a mechanism involving an electron transfer reaction is postulated. 相似文献
12.
R. Mercadé-Prieto R. Allen D. York J. A. Preece T. E. Goodwin Z. Zhang 《Experimental Mechanics》2012,52(9):1435-1445
The encapsulation of liquids within an external wall or shell is an important technology often utilized in the production of many commercial products. The mechanical characterization of such microcapsules is paramount in order to fully understand their performance in their target environment. Some microcapsules, with wall materials such as inorganic based compounds, rupture at small deformations, commonly near the elastic regime. The study herein presents a general methodology that enables calculation of the failure stresses leading to the elastic-like rupture of microcapsules under parallel compression testing. Two scenarios of failure, brittle and ductile, were considered. Analyses of the critical stresses present within the microcapsule wall during different degrees of fractional deformation were obtained using finite element modelling, resulting in similar values for both the brittle and ductile scenarios. The correlations presented were used to determine the failure stresses of tetraethoxyorthosilane-methyltrimethoxysilane (TEOS-MTMS) microcapsules with a model core oil, which are 11?C14?±?10?MPa. The data were further analyzed using Weibull distributions. 相似文献
13.
Conrad A. P. Goodwin Dr. Floriana Tuna Prof. Eric J. L. McInnes Prof. Stephen T. Liddle Dr. Jonathan McMaster Dr. Inigo J. Vitorica‐Yrezabal Dr. David P. Mills 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14579-14583
We report the synthesis and characterization of the uranium(III) triamide complex [UIII(N**)3] [ 1 , N**=N(SiMe2tBu)2?]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three‐coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N“)3] (N”=N(SiMe3)2?), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N“)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single‐molecule magnets. 相似文献
14.
S. Spall A. A. Goodwin M. D. Zipper G. P. Simon 《Journal of Polymer Science.Polymer Physics》1996,34(14):2419-2431
The dynamic mechanical and dielectric spectra of a miscible polyester and polycarbonate blend are investigated with emphasis on the latter technique. It was found that relaxation spectra for the blends from both techniques are broader than those of the constituent homopolymers. This is ascribed to greater intermolecular coupling and concentration fluctuations within the blends. The composition at which the greatest coupling occurs is dependent on the relaxation technique used and is skewed towards the component which shows the highest degree of intermolecular coupling. A number of parameters, such as relaxation time of the polymer molecules in the blend and relaxation strength, are compared as a function of reduced temperature (experimental temperature scaled by the glass transition temperature). Whereas blend behavior is generally intermediate between that of the homopolymers, it appears as though mobility of compositions with low polyester content have a greater relaxation time and possess a higher activation energy when compared to a simple, weighted average of the corresponding homopolymer values. © 1996 John Wiley & Sons, Inc. 相似文献
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The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material has been investigated by reverse Monte Carlo (RMC) modeling of neutron total scattering data. We obtain, for the first time, quantitative measurements of the extent to which the and polyhedra move as rigid units, and we show that these values are consistent with the predictions of rigid unit mode theory. We suggest that rigid unit modes are associated with the NTE. Our results do not support a recent interpretation of x-ray-absorption fine structure spectroscopy data in terms of a larger rigid structural component involving the Zr-O-W linkage. 相似文献
18.
We describe a model-independent approach for the extraction of detailed lattice dynamics information from neutron powder diffraction data, based on a statistical analysis of atomistic configurations generated using reverse Monte Carlo structural refinement. Phonon dispersion curves for MgO extracted in this way are shown to reproduce many of the important features found in those determined independently using neutron triple-axis spectroscopy. By means of molecular dynamics simulations, we quantify the extent to which the diffraction data are sensitive to lattice dynamics in this system. 相似文献
19.
(3R)- and (3S)-Deuteriated forms of 5-aminolaevulinic acid have been synthesized and the (3R)-form shows a significantly larger isotope effect when incubated with porphobilinogen synthase from bovine liver and from Bacillus subtilis; based on this and on available crystal structures, a modified mechanism for the enzymic reaction is proposed. 相似文献
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