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Abstract
The helicene, pyrido[3,2-f]quinolino[6,5-c]cinnoline 5-oxide, was prepared by treatment of 6-hydroxylaminoquinoline with xanthine oxidase or treatment of 6-nitroquinoline with glucose in 30% NaOH and the product characterized using NMR, high resolution mass spectrometry, and X-ray crystallography. The hydrogens on carbons 7 and 12 of the terminal aromatic rings are separated by 2.495 ? creating an angle of 25.0° between the planes of the two quinoline ring systems. In the crystal, water molecules serve to link the helicenes into a one dimensional chain structure forming a hydrogen bonded bridge between N2 of one molecule and N4 of another. The molecule (C18H10N4O·H2O) crystallized in the monoclinic P21/n space group. Unit cell parameters for pyrido[3,2-f]quinolino[6,5-c]cinnoline 5-oxide monohydrate: a = 7.0829(12), b = 18.559(3), c = 11.0985(19) ?, β = 107.736(2)°, and Ζ = 4. 相似文献3.
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A. P. S. Selvadurai R. K. N. D. Rajapakse 《International Journal of Solids and Structures》1985,21(12)
The present paper examines the problems related to the axial, lateral, and rotational loading of a rigid cylindrical inclusion which is embedded in bonded contact at the boundary of an isotropic elastic half space. The rigid inclusion is modeled as a field of distributed forces which represent the normal and shear tractions that act on the inclusion-elastic-medium interface. The intensities of these distributed tractions are determined by enforcing displacement compatibility conditions at discrete locations of the interface. These compatibility conditions are derived from rigid-body displacement modes appropriate for each loading. The results derived from this numerical scheme are compared with equivalent results derived via analytical techniques which focus on the solution of the governing integral-equation schemes and other approximate-solution schemes. The numerical results presented in the paper illustrate the manner in which the generalized stiffnesses of the embedded inclusion are influenced by its geometry and Poisson's ratio of the half-space region. 相似文献
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Regions of low oxygen concentration (hypoxia) occur in both normal human physiology and under pathophysiological conditions. Fluorescent probes for the direct imaging of cellular hypoxia could be useful tools that complement radiochemical imaging and immunohistochemical staining methods. In this work, we set out to characterize the hypoxia-selective enzymatic metabolism of a simple nitroaryl probe, 6-nitroquinoline (1). We envisioned that this compound might undergo hypoxia-selective, bioreductive conversion to the fluorescent product, 6-aminoquinoline (2). The probe 1 was, indeed, converted to a fluorescent product selectively under hypoxic conditions by the one-electron reducing enzyme NADPH:cytochrome P450 reductase. However, inspection of the fluorescence spectrum and LC-MS analysis of the reaction mixture revealed that the expected product 2 was not formed. Rather, the 63-fold increase in fluorescence emission at 445 nm resulting from the hypoxic metabolism of 1 was due to formation of the azoxy-helicene product, pyrido[3,2-f]quinolino[6,5-c]cinnoline 3-oxide (4). The generation of 4 involves an unusual biaryl bond formation under reductive conditions. The mechanism of this process remains uncertain but could proceed via combination of a nitroaryl radical anion with a neutral nitrosoaryl radical, followed by tautomerization and intramolecular condensation between the resulting hydroxylamine and nitroso functional groups. Bioreductive metabolism of nitroaryl compounds represents a promising strategy for the selective delivery of cytotoxic agents and fluorescent markers to hypoxic tissue, but the results described here provide an important glimpse of the chemical complexity that can be associated with the enzymatic one-electron reduction of nitroaryl compounds. 相似文献
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Shackelford SA Anderson MB Christie LC Goetzen T Guzman MC Hananel MA Kornreich WD Li H Pathak VP Rabinovich AK Rajapakse RJ Truesdale LK Tsank SM Vazir HN 《The Journal of organic chemistry》2003,68(2):267-275
A new one-pot nitration employing tetramethylammonium nitrate and trifluoromethanesulfonic anhydride in dichloromethane to provide a ready source of the nitronium triflate nitrating agent is presented. Rapid and selective nitration with a variety of aromatic and heteroaromatic substrates is achieved resulting in the synthesis of several novel organic compounds. A distinct advantage is the removal of undesired byproducts by aqueous workup. This very mild nitration permits large-scale syntheses and gives high isolated product yields that often require no further purification. This tetramethylammonium nitrate-based nitration also has been applied to microwave-assisted conditions, and the results with several compounds are outlined. 相似文献
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Effect of electric boundary conditions on crack propagation in ferroelectric ceramics 总被引:1,自引:1,他引:0
In this paper, the effect of electric boundary conditions on Mode I crack propagation in ferroelectric ceramics is studied by using both linear and nonlinear piezoelectric fracture mechanics. In linear analysis, impermeable cracks under open circuit and short circuit are analyzed using the Stroh formalism and a rescaling method. It is shown that the energy release rate in short circuit is larger than that in open circuit. In nonlinear analysis, permeable crack conditions are used and the nonlinear effect of domain switching near a crack tip is considered using an energy-based switching criterion proposed by Hwang et al.(Acta Metal. Mater.,1995). In open circuit, a large depolarization field induced by domain switching makes switching much more diffcult than that in short circuit. Analysis shows that the energy release rate in short circuit is still larger than that in open circuit, and is also larger than the linear result. Consequently,whether using linear or nonlinear fracture analysis, a crack is found easier to propagate in short circuit than in open circuit, which is consistent with the experimental observations of Kounga Njiwa et al.(Eng. Fract. Mech., 2006). 相似文献