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41.
From flash photolysis data of benzil and 2,2′-dichlorobenzil, the role of conformeric triplets in the formation of hydrogen
adduct radicals has been discussed. The planar relaxed triplet absorbing at 470 nm is less efficient in forming a hydrogen
adduct radical as compared to its puckered conformeric partner. Among the hydrogen donors, triethyl amine and isopropanol,
the former is more efficient in converting puckered triplets and less efficient in the case of planar conformers. Absorptions
of radicals and radical anions of 2,2′-dichlorobenzil appear at 355 nm and 460 nm respectively. These are blue-shifted as
compared to those of the parent compound benzil appearing at 370 nm and 540 nm, respectively. This blue-shift has been discussed
in terms of steric hindrance due to ortho-substitution. 相似文献
42.
架起传统与现代的桥梁--建筑历史与理论课程体系教学改革的思考 总被引:2,自引:0,他引:2
邱枫 《宁波大学学报(理工版)》2004,17(4):485-488
重新审视建筑历史理论教学的目标、内容、教学方式和手段,通过对国内几座有影响的建筑院校的调研,比较各个院校在这些问题及途径上的异同,分析其利弊,以期促进建筑历史与理论课程体系教学的建设和改革. 相似文献
43.
The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pKa are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C18‐bonded packing materials, including the 5 μm Xterra‐C18 (121 Å), 5 μm Gemini‐C18 (110 Å), 5 μm Luna‐C18(2) (93 Å), 3.5 μm Extend‐C18 (80 Å), and 2.7 μm Halo‐C18 (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant WWpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pKa and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution. 相似文献
44.
Reduction of tetranuclear heterometallic complex Mo2Mg2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex
[MoVIO2Mg(MeOH)2(OMe)4]2 and a partially reduced MoV complex are in good agreement with experimental data. The reduced MoIII complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with
release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of
the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008. 相似文献
45.
A new numerical method called linearized and rational approximation method is presented to solve non‐linear evolution equations. The utility of the method is demonstrated for the case of differentiation of functions involving steep gradients. The solution of Burgers' equation is presented to illustrate the effectiveness of the technique for the solution of non‐linear evolution equations exhibiting nearly discontinuous solutions. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
46.
This paper presents the applications of digital image correlation technique to the mesoscopic damage and fracture study of
some granular based composite materials including steelfiber reinforced concrete, sandstone and crystal-polymer composite.
The deformation fields of the composite materials resulted from stress localization were obtained by the correlation computation
of the surface images with loading steps and thus the related damage prediction and fracture parameters were evaluated. The
correlation searching could be performed either directly based on the gray levels of the digital images or from the wavelet
transform (WT) coefficients of the transform spectrum. The latter was developed by the authors and showed higher resolution
and sensitivity to the singularity detection. Because the displacement components came from the rough surfaces of the composite
materials without any coats of gratings or fringes of optical interferometry, both surface profiles and the deformation fields
of the composites were visualized which was helpful to compare each other to analyze the damage of those heterogeneous materials.
The project supported by the National Natural Science Foundation of China (10125211 and 10072002), the Scientific Committee
of Yunnan Province for the Program of Steel Fiber Reinforced Concrete, and the Institute of Chemical Materials, CAEP at Mianyang 相似文献
47.
H. Stephani 《General Relativity and Gravitation》2003,35(3):467-474
An intuitive definition of standing gravitational waves is proposed. Some main classes of exact vacuum solutions are searched for standing gravitational waves, in most cases with a negative result. Only some Einstein–Rosen waves meet the conditions. 相似文献
48.
Dielectric elastomer actuators (DEAs) have received considerable attention recently due to large voltage-induced strains, which can be over 100%. Previously, a large deformation quasi-static model that describes the out-of-plane deformations of clamped diaphragms was derived. The numerical model results compare well with quasi-static experimental results for the same configuration. With relevance to dynamic applications, the time-varying response of initially planar dielectric elastomer membranes configured for out-of-plane deformations has not been reported until now. In this paper, an experimental investigation and analysis of the dynamic response of a dielectric elastomer membrane is reported. The experiments were conducted with prestretched DEAs fabricated from 0.5 mm thick polyacrylate films and carbon grease electrodes. The experiments covered the electromechanical spectrum by investigating membrane response due to (i) a time-varying voltage input and (ii) a time-varying pressure input, resulting in a combined electromechanical loading state in both cases. For the time-varying voltage experiments, the membrane had a prestretch of three and was passively inflated to various predetermined states, and then actuated. The pole strains incurred during the inflation were as high as 25.6%, corresponding to slightly less than a hemispherical state. On actuation, the membrane would inflate further, causing a maximum additional strain of 9.5%. For the time-varying pressure experiments, the prestretched membrane was inflated and deflated mechanically while a constant voltage was applied. The membrane was cycled between various predetermined inflation states, the largest of which was nearly hemispherical, which with an applied constant voltage of 3 kV corresponded to a maximum polar strain of 28%. The results from these experiments reveal that the response of the membrane is a departure from the classical dynamic response of continuum membrane structures. The dynamic response of the membrane is that of a damped system with specific deformation shapes reminiscent of the classical membrane mode shapes but without same-phase oscillation, that is to say all parts of the system do not pass through the equilibrium configuration at the same time. Of particular interest is the ability to excite these deformations through a varying electrical load at constant mechanical pressure. 相似文献
49.
The development of perturbations of the parameters of a dense gaseous envelope traveling with an acceleration driven by a difference in the pressures on either side is investigated numerically. Plane and axisymmetric time-dependent flows of a compressible medium are considered. The effect of both the density of the envelope and the form of the initial perturbations of its shape and motion on the mass cumulation in the compactions formed is studied. The evolutions of the perturbations of a layer and the surface of a contact discontinuity accelerated by an impinging plane shock wave are compared. 相似文献
50.
Michael C. W. Chan Dr. 《化学:亚洲杂志》2008,3(1):18-27
The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???Hβ ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis. 相似文献