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3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3). 相似文献
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Birefringence changes due to thermal expansion have been calculated for anthracene and phenanthrene. The method assumes that the effective molecular polarizability calculated at room temperature is constant in the molecular axis system for small changes of molecular orientation and separation. For anthracene, the calculations reproduce the observed birefringence change quantitatively. For phenanthrene, two thirds of the observed change is due to thermal expansion, the rest to structural alterations at the 70°C phase transition; transition to a Pa structure is ruled out. Birefringence calculations could be used to test other high-temperature structures for phenanthrene which might be suggested by lattice-energy calculations. 相似文献
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A spectroelectrochemical (SEC) assay for uric acid in human urine has been developed that is essentially reagent-free and involves relatively short analysis times of ∼12 min per specimen using a single-point standard addition approach. The SEC method was demonstrated to be selective for uric acid in human urine, avoiding interference through both the usual control parameters (electrolysis potential and measurement wavelength) and the relatively slow kinetics of a post-electrolysis reaction involving the oxidation product. Results from the SEC analysis of a split set of human urine specimens were well correlated to those obtained using a standard high-performance liquid chromatography method, suggesting the feasibility of clinical applications. 相似文献
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M.H. Majles Ara SR. Hosseini M.H. Rezvani M. Abolhassani 《Journal of Physics and Chemistry of Solids》2011,72(11):1367-1372
In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO3 photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering. 相似文献
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Zulma Jiménez Christopher Bounds Charles E. Hoyle Andrew B. Lowe Hui Zhou John A. Pojman 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):3009-3021
Polymerizable ionic liquids were synthesized from the neutralization reaction between trialkylamines (tributylamine, trihexylamine, trioctylamine, 2‐(dimethyl‐amino)ethyl acrylate, and 2‐(dimethylamino)ethyl methacrylate) and acid‐containing (meth)acrylates to study the kinetics of their photopolymerization. The ionic liquids formed from acrylic acid and methacrylic acid with trialkylamines showed low or moderate increases in rate compared to their monofunctional analogues. The ionic liquids formed from (meth)acrylic acid and a tertiary amine with a pendant acrylate exhibited rates typical of traditional di(meth)acrylates, although the (meth)acrylates were not covalently attached to the same molecule. All of the phosphate‐based ionic liquids exhibited very rapid polymerization rates and strong dependence on the initial viscosity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3009–3021, 2007 相似文献
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MA Freitas SR Dillon RC Dougherty AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1622-1625
The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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The Fourier transform method and submolecule treatment described previously are used to derive an exact expression for the change ΔP in polarization energy of a localized charge when some of the surrounding molecules have polarizabilities different from those in the perfect crystal. The crystal structure is assumed unchanged. The method can be applied to vacancies, charged exciton complexes and X traps. It is illustrated by calculations of ΔP for isolated unrelaxed vacancies in anthracene. If the charge is not too near the vacancy, ? ΔP equals the charge-induced-dipole energy in an isotropic continuum having the average dielectric constant for anthracene. 相似文献