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91.
Shih‐I Lu 《Journal of computational chemistry》2009,30(14):2176-2180
In this article, we examined the Gibbs energy of activation for the Z/E thermal isomerization reaction of (1Z)‐acetaldehyde hydrazone and (1Z)‐acetaldehyde N,N‐dimethylhydrazone, at 298.15 K in the solvent of cyclohexane. We carried out computations employing both the Gaussian‐4 (G4) theory and the coupled cluster method using both single and double substitutions and triple excitations noniteratively, CCSD(T). The CCSD(T) energy is extrapolated to the complete basis set (CBS). We compared the calculated results to the available experimental observation. It appeared that both G4 and CCSD(T)/CBS computations overestimated the experimental value by as much as about 6 and 12 kcal/mol in the present two cases. We discussed possible sources of error and proposed the experimental kinetic data could be questionable. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 相似文献
92.
A system of reaction–diffusion equations which governs the propagation of an ozone decomposition laminar flame in Lagrangian co-ordinates is analysed by means of compact operators and modified equation methods. It is shown that the use of fourth-order accurate compact operators yields very accurate solutions if sufficient numbers of grid points are located at the flame front, where very steep gradients of temperature and species concentrations exist. Modified equation methods are shown to impose a restriction on the time step under certain conditions. The solutions obtained by means of compact operators and modified equation methods are compared with solutions obtained by other methods; good agreement is obtained. 相似文献
93.
Yi-Chun Chen Jin-Ming Chen Chia-Haw Hsu Jyh-Fu Lee Jien-Wei Yeh Han C. Shih 《Solid State Ionics》2009,180(20-22):1215-1219
Recently, lithium bi-metal phosphates (LiM′M″PO4) have been synthesized for use as cathode materials in order to increase cell voltages and electrical performances. In this work, we have substituted Mn2+ at the 4c site of LiFePO4 to prepare the lithium bi-metal phosphate LiMn0.25Fe0.75PO4 and have found that it greatly enhances the cell voltage. At a 0.05 C discharge rate, the cell capacity was about 153 mAhg− 1 and the average working voltage rose to 3.53 V due to the Mn substitution. However, the capacity and working voltage both decrease as the discharge rate increases. By in-situ metal K-edge absorption analysis, it reveals that the substituted metal Mn2+ does not work completely at a higher discharge rate, due to poor electrical conductivity and a serious Jahn–Teller effect. 相似文献
94.
95.
H. -H. Lei P. P. T. Sah und Ch. Shih 《Fresenius' Journal of Analytical Chemistry》1937,109(3-4):135-136
Ohne Zusammenfassung 相似文献
96.
97.
A twisted nematic pi-cell has been studied by optical transmission measurement, polarized Fourier-transform infrared (pFTIR) absorption spectroscopy, and Raman spectroscopy. Our pFTIR results suggest that the LC molecules undergo a restricted rotation about the molecular long axis. The rise and decay times of the optical response were found to be 6 ms and 1.6 ms, respectively. The switching dynamics of the twisted pi-cell was also studied using time-resolved Raman spectroscopy. A normal mode associated with the C-H out-of-plane wag on the LC core was found to be enhanced after the electric field was switched off. Our data show that LC molecules in the twisted pi-cell do not rotate like a rigid molecule during the field-induced reorientation process. The methods employed in this study have yielded valuable information about LC alignment and field-induced reorientation with respect to functional group specificity. 相似文献
98.
Shih Hsi Chu Zhi Hao Chen Zun Yao Weng Elizabeth C. Rowe Edward Chu Ming-Yu Wang Chu 《Journal of heterocyclic chemistry》1987,24(4):989-995
Amino analogs of BAU (5-benzylacyclouridine) and BBAU (5-benzyloxybenzylacyclouridine) and their 2′-hydroxymethyl derivatives were synthesized for evaluation as inhibitors of uridine phosphorylase and hence potential cancer chemotherapeutic agents. Both aminomethyl analogs were found to be potent inhibitors of this enzyme and good potentiators of the anti-tumor action of FUdR. 相似文献
99.
Pyrogallol (1,2.3-benzentriol, 1 ) reacts with dioxygen in weakly alkaline solutions to form purpurogallin (2,3,4,6-tetrahydroxy-5H-benzocycloheptene-5-one, 2 ) which then reacts to form purpurogalloquinone ( 3 ) which then decays to a product absorbing at 440 nm. The formation of 3 requires 1.5 mol O2 per mol 1 , and 1.0 mol per mol 2 . No O2 is consumed during the decay of 3 , and this reaction, being insensitive to O2 concentrations and the presence of both superoxide dismutase (SOD) and catalase, does not appear to be an oxidation. The first-order rate of decay of 3 decreases with increasing pH. 1 and 3 react at pH 9.0 with a second-order rate constant of ca. 100 M?1 s?1. SOD inhibits the oxidation of 1 and 2 . Slight and variable apparent inhibition of the oxidation of 2 and 3 by SOD may be due to trace impurities in 2 , but not contamination by 1 . The peak concentration of 3 is attained more rapidly during the oxidation of 1 than during the oxidation of 2 . A kinetic scheme based on parallel oxidation of 1 by dioxygen and superoxide, and it which the semiquinone of 1 oxidizes 2 , is partially successful in simulating the observed kinetic behavior. 相似文献
100.
Jui-Hao Wang Teng-Kai Shih Chia-Fu Chen Kuang-Chung Chen Chien-Chung Chen Wha-Tzong Whang G. Steven Huang Hsiang-Yi Su 《Optics Communications》2008,281(15-16):3953-3956
Back-surface diffusive reflectors have been widely applied in many optical systems to promote the efficiency used in system. In this work, we propose a novel way to fabricate a soft diffusive reflector by using of silicone (polydimethylsiloxane, PDMS). High-reflectance substrates were first fabricated by mixing nanoscaled TiO2 powders with PDMS polymers, and then microscale wave-like undulations were spontaneously developed after the substrates were dipped into H2SO4/HNO3 solutions. After optical examination, a TiO2/PDMS plate comprising microscale undulations, which can surely serve as a reflector, could reflect and diffuse light effectively. Besides, all fabrication processes can be executed in the ambient environment and at low temperature. This proposed method has a potential for mass production in the future. 相似文献