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41.
Watson William H. Kashyap Ram P. Krawiec Mariusz Marchand Alan P. Tsay Fuh-Rong 《Structural chemistry》1994,5(1):21-35
5-Methyl-2-phenylpentacyclo[5.4.0.02, 6.03, 10.05, 9]undecane-8, 11-dione,5-methyl-2-phenylpentacyclo [5.4.0.02,6.03,10.05,9]undecane-8-one-11-ol,and 5-methyl-2-phenylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-diol are three cage compounds which differ only in the oxidation state at C(8) and C(11). The three compounds contain a four-membered, a six-membered, and four five-membered rings fused into a cagelike structure. An X-ray structure analysis shows the C(1)-C(7) and C(9)-C(10) bonds in the diketo cage to be 1.606(2) and 1.586(2) Å, which are significantly longer than in the other two molecules. In order to assess the effects of strain, steric, and electronic factors in these compounds, we investigated the unsubstituted parent cage compounds and a series of derivatives by molecular mechanics (MM3), AMPAC (AM1), MOPAC (PM3), and GAUSSIAN 90 calculations. These data suggest that dipolar through space interactions are responsible for the bond elongation and not a
–
* interaction, which has been postulated in parallel-systems originating from a common bond. A small degree of
–
* through-bond interaction may contribute to the lengthening in the dimethylene cage analogues. 相似文献
42.
Time-resolved coherent anti-Stokes Raman experiments are reported for the benzene crystal 991 cm?1 mode and in mixed C6H6/C 6D6 crystals. Addition of C6D6 results in an increase in the rate at which the excitation is trapped. This is explained by the recent theory of Velsko and Hochstrasser which predicts that the trapping rate should undergo a maximum at some isotopic impurity concentration, consistent with observations from time and frequency domain studies. A proper convolution procedure for CARS experiments in the time domain is presented. 相似文献
43.
Yun Chen Cherng-Jing Tsay 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1319-1327
The monomer, trans-2,2′-dihydroxystilbene (DHS), has been prepared by asymmetric photocleavage (254 nm) of coumarin dimer acid derived from coumarin dimer. Four new polyesters are successfully synthesized by interfacial polycondensation of the DHS with adipoyl chloride, azelaoyl chloride, sebacoyl chloride, and dodecanedioyl dichloride, respectively. The reduced viscosities of the polyesters decrease from 0.32 to 0.11 dL/g as the number of methylene unit in diacid chlorides increases from 4 to 10. From DSC investigation, it is found that the polyesters are semi-crystalline polymers with Tm = 39–192°C. Under 350 nm light, photocrosslinking behavior in solution and film-state is investigated by UV spectral change with irradiation time (350 nm). The photoreactive stilbene chromophores in the main chain dimerize to form cyclobutane derivatives, and lead to crosslinking of the polyesters. Photosensitivity in the film state has also been evaluated by their characteristic curves. Polyester from dodecanedioyl dichloride ( 5d ) exhibits the highest initial reaction rate and ultimate crosslinking ratio. © 1995 John Wiley & Sons, Inc. 相似文献
44.
The secondary structure of the C-terminal fragment (10 kDa) of rat hsc70 (a. a. #546–646) was analyzed according to circular dichroism spectra. In the pH range 5–9 and at concentrations of Na+ up to 0.18 M, the protein is estimated to contain 32-34% a helix, 18–16% of β sheet, approximately 25% for both turns and disordered structures. This protein is most stable at pH between 6 and 7 in solution with 0.055 M Na+ concentration. However, all Tm are relatively large (57–73 °C) and alterations from one condition to another are small. Thus, the C-fragment (10 kDa) of hsc70 is a stably folded protein under physiological conditions. 相似文献
45.
Jih Ru Hwu Prof. Joseph Jen‐Tse Huang Dr. Fu‐Yuan Tsai Dr. Shwu‐Chen Tsay Dr. Ming‐Hua Hsu Dr. Kuo Chu Hwang Dr. Jia‐Cherng Horng Dr. Ja‐an Annie Ho Dr. Chun‐Cheng Lin Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(35):8742-8750
N‐Nitroso compounds containing benzene, fluorene or fluorenone rings were synthesized. Photolysis of these compounds with 312‐nm UV light provided the NO . species, the presence of which was corroborated by use of an EPR method and of 2‐phenyl‐4,4,5,5‐tetramethylimidazolin‐1‐oxyl 3‐oxide (PTIO) as a trapping agent. During irradiation of N‐methyl‐N‐nitroso‐9‐fluorenone carboxamide ( 14 c ) in the absence of PTIO, it underwent decomposition followed by recombination to give the heterocyclic nitric oxide radical 15 . Incorporation of intercalating moieties endowed the N‐nitroso compounds with DNA‐cleaving ability through single‐strand scission upon UV irradiation in a phosphate buffer (pH 5.0–8.0) under aerobic conditions. 相似文献
46.
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48.
We present a calculation of the band structure of semiconducting crystals under arbitrarily high stress, in which all input parameters are determined from the properties of the unstressed crystal alone. The method is applied to obtain the band structure of Ge and Si at high stress, and the strain dependence of the energies and matrix elements of a number of critical-point transitions are presented. 相似文献
49.
50.
Tidal Effects on Groundwater Motions 总被引:1,自引:0,他引:1
Assuming a sharp interface between freshwater and seawater within a coastal aquifer, a theory is developed to account for the piezometric head movement of steady and unsteady components in terms of large- and small-time scales. Tidal fluctuations are simulated by a series of decomposed simple harmonic motions in time. Groundwater fluctuation induced by tidal motion is perturbed to the groundwater head of large-time scale. Ghyben–Herzberg formulation is applied for solutions of large-time scale and a unified formulation for various flows of small-time scale is derived (Strack, 1989). Approximate analytical solutions for amplitudes and phase lags of tidal groundwater motions and the freshwater–seawater interface for a coastal aquifer in a circular island are obtained. The induced fluctuation amplitude generally decays in distance with a parameter consisting of hydraulic conductivity, storage coefficient, thickness of aquifer and tidal period. The present approach can be applied to confined and unconfined aquifers, with only freshwater flows or interfacial flows. The theory is verified with some experimental results (Parlange, et al., 1984; Nielson, 1990). It can also used to determine physical parameters of an aquifer by monitoring the groundwater fluctuations due to tidal motions (Carr and van der Kamp, 1969). 相似文献