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31.
Zahid H. Khan 《International journal of quantum chemistry》1992,42(6):1717-1735
Electronic transition energies of radical cations of 1.2-, 1.3-, 1.6-, and 1.7?dihydroxynaphthalenes are calculated using an open-shell SCF method with configuration interaction. The results are critically analyzed and a correlation diagram is given that shows the energy-shift and intensity variation in the electronic transitions when moving from one system to another, thus revealing the characteristic behavior of the transitions depending on the positions of the hydroxyl substituents. An interesting relation connecting the electronic spectroscopy with the UV photoelectron spectroscopy is suggested on the basis of which the first ionization potentials (IPS ) of the substituted aromatic systems can be inferred from the calculated energy of the A-type (HOMO → LUMO ) transitions for their radical cations. Furthermore, the predictability of the IP s is found to be considerably increased with the incorporation of “molecular size” in the regression. 相似文献
32.
Effects of relative humidity conditions in the irradiation chamber and of temperature of the chamber on the response of 3 mm thick light blue poly (methyl methacrylate) sheets have been studied. The response was measured spectrophotometrically at 402, 450, 596 and 612 nm. The response of the dosimeter is independent of the relative humidity (12–97%) during irradiation if the response is measured within 24 h of irradiation. If the response is measured after longer storage time, the absorbance at 402 and 450 nm increases significantly. At these two wavelengths the response of the dosimeter is also independent of the temperature of the irradiation chamber in the range of 0 to 40 °C. However, at higher temperatures (60, 80 °C), the response is not uniform. 相似文献
33.
In a weakly acidic solution, the addition of HBr to 1-phenylprop-1-yne produces predominantly the anti-Markovnikov product. In this paper, we consider five possible explanations for this behavior and conclude that the concerted addition is occurring on the acetylenic pi bond orthogonal to the extended aromatic pi system. The electronic effect of the distal methyl group and the steric hindrance of the coplanar phenyl ring combine to promote bromide attack at the beta carbon. Attack on this pi bond is insensitive to the electronic effect of meta and para substituents on the ring but is very (sterically) sensitive toward all ortho substituents. 相似文献
34.
Structural characterization of nanosized CeO(2)-SiO(2), CeO(2)-TiO(2), and CeO(2)-ZrO(2) catalysts by XRD, Raman, and HREM techniques 总被引:1,自引:0,他引:1
Reddy BM Khan A Lakshmanan P Aouine M Loridant S Volta JC 《The journal of physical chemistry. B》2005,109(8):3355-3363
Structural characteristics of nanosized ceria-silica, ceria-titania, and ceria-zirconia mixed oxide catalysts have been investigated using X-ray diffraction (XRD), Raman spectroscopy, BET surface area, thermogravimetry, and high-resolution transmission electron microscopy (HREM). The effect of support oxides on the crystal modification of ceria cubic lattice was mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahighly dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO(2)-SiO(2) sample primarily consists of nanocrystalline CeO(2) on the amorphous SiO(2) surface. Both crystalline CeO(2) and TiO(2) anatase phases were noted in the case of CeO(2)-TiO(2) sample. Formation of cubic Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) (at 1073 K) were observed in the case of the CeO(2)-ZrO(2) sample. Raman measurements disclose the fluorite structure of ceria and the presence of oxygen vacancies/Ce(3+). The HREM results reveal well-dispersed CeO(2) nanocrystals over the amorphous SiO(2) matrix in the cases of CeO(2)-SiO(2), isolated CeO(2), and TiO(2) (anatase) nanocrystals, some overlapping regions in the case of CeO(2)-TiO(2), and nanosized CeO(2) and Ce-Zr oxides in the case of CeO(2)-ZrO(2) sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO(2) is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of the mixed oxide systems is more than that of pure CeO(2) and is system dependent. 相似文献
35.
Shah BH Siddiqui A Qureshi KA Khan M Rafi S Ujan VA Yakoob MY Yaqub Y Rasheed H Saeed SA 《Experimental & molecular medicine》1999,31(1):42-46
Our previous studies have shown that subthreshold concentrations of two platelet agonists exert synergistic effects on platelet aggregation. Here we studied the mechanism of synergistic interaction of 5-hydroxytryptamine (5-HT) and epinephrine mediated platelet aggregation. We show that 5-HT had no or little effect on aggregation but it did potentiate the aggregation response of epinephrine. The synergistic interaction of 5-HT (1-5 microM) and epinephrine (0.5-2 microM) was inhibited by alpha2-adrenoceptor blocker (yohimbine; IC50= 0.4 microM), calcium channel blockers (verapamil and diltiazem with IC50 of 10 and 48 mM, respectively), PLC inhibitor (U73122; IC50=6 microM) and nitric oxide (NO) donor, SNAP (IC50=1.6 microM)). The data suggest that synergistic effects of platelet agonists are receptor-mediated and occur through multiple signalling pathways including the activation PLC/Ca2+ signalling cascades. 相似文献
36.
V. A. Khan Yu. V. Gatilov Zh. V. Dubovenko V. A. Pentegova 《Chemistry of Natural Compounds》1979,15(5):572-576
An x-ray structural investigation has been made of a new sesquiterpene alcohol — koraiol — in the form of its complex with pyridine (2:1). The cyclobutane rings are nonplanar and the foldings of rings A and B amount to 17 and 31°, respectively. The seven-membered ring has the chair form. 相似文献
37.
Imtiaz Ahmad M. Arsala Khan M. Shakirullah M. Ishaq Yousaf Iqbal Saeed ur Rehman 《中国化学会会志》2004,51(4):729-734
Influence of pretreatments, i.e., demineralization and pre‐soaking in some solvents on the yields of liquefied products obtained from hydro‐depolymerization of Pakistani coal in a pool of hydrogen has been discussed. Results of hydrogenation experiments demonstrated that demineralizing the coal sample prior to liquefaction caused the yields to decrease compared with the virgin coal samples. The contribution of mineral matter of coal has been evaluated by comparing the yields of liquid products of virgin and leached samples. Increase in the yields obtained from the hydrogenation experiments of swollen coal samples was not satisfactorily significant. 相似文献
38.
A rapid access to 7-azaspiro[4.5]decan-6-ones 1 involving three regio- and chemoselective reactions starting from tetrabromonorbornyl derivatives is described. The alkaline H(2)O(2) cleavage reaction of monosubstituted alpha-diketones 9 furnished the potential bridged bicyclic lactones 10in a highly regio- and stereoselective manner. The radical-mediated, intermolecular bridgehead C-C bond formation of the versatile bridged lactones 10 with acrylonitrile followed by LAH reduction of the adduct 13 intriguingly leads to the formation of novel spirolactam building blocks 1. 相似文献
39.
Eberhard Bothe Helmut Gorner Joachim Opitz Dietrich Schulte-Frohlinde Aslam Siddiqi Malgorzata Wala 《Photochemistry and photobiology》1990,52(5):949-959
Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA. 相似文献
40.
The molar conductances of dilute solutions of salicylic and monochloroacetic acids in binary mixtures of methanol, ethanol, 1-propanol, N,N-dimethylformamide, acetone, acetonitrile, tetrahydrofuran and dioxane with water have been measured at 25°C. The Lee-Wheaton conductance equation was fitted to the data in order to derive thermodynamic dissociation constants and limiting molar conductances. The results were compared with those in the literature pertaining to analogous media, mostly derived potentiometrically. The findings are interpreted in terms of a solvent effect on the ionization of these acids in mixed solvent systems.This paper is dedicated to the late Professor Raymond M. Fuoss on his 3rd anniversary. 相似文献